Co-reporter:Hu Zhou, Qi Chen, Ai-Hua Yuan, Hong-Bo Zhou, Xiao-Ping Shen, Lei Chen, and You Song
Crystal Growth & Design December 6, 2017 Volume 17(Issue 12) pp:6523-6523
Publication Date(Web):October 25, 2017
DOI:10.1021/acs.cgd.7b01196
The slow diffusion reaction of octacyanometalate [W(CN)8]3–, lanthanide ions, and 4,4′-bipyridyl-N,N′-dioxide (bpdo) has generated a series of isostructural three-dimensional pillared-layer networks with general formula [Ln(bpdo)1.5(H2O)W(CN)8]·0.5CH3OH·6H2O (Ln = Dy–Yb, Gd), in which Ln(III) atoms adopted an unusual seven-coordinated geometry in the cyanometalate-based lanthanide system. This building approach on the basis of the simultaneous employment of cyanide and bpdo bridges offers potential possibilities for designing and constructing 5d-4f coordination networks with high dimensionalities. Interestingly, the LnIII-bpdo-WV(CN)8 system has undergone an unique two-step phase transition upon prolonging the diffusion reaction time, together with the structural changing from initial ion pair through two-dimensional layer to final three-dimensional pillared-layer network. Magnetic studies of all compounds revealed typical and dominant single-ion magnetic behaviors over the weak coupling interactions between spin centers.
Co-reporter:Wenqing Wang, Jing Li, Lei Yin, Yue Zhao, Zhongwen Ouyang, Xinping Wang, Zhenxing Wang, You Song, and Philip P. Power
Journal of the American Chemical Society August 30, 2017 Volume 139(Issue 34) pp:12069-12069
Publication Date(Web):August 8, 2017
DOI:10.1021/jacs.7b06795
Chemical oxidations of piano-stool chromium/cobalt carbonyl complexes Cr(CO)3(η6,η5-C6H5C5H4)Co(CO)2 (1) and Cr(CO)3(η6,η6-C6H5C6H5) Cr(CO)3 (2) were investigated. Upon one-electron oxidation, 1 was transformed to a heterometalloradical species, 1•+. However, either one- or two-electron oxidation of 2 afforded a decomposition product, 3. Dipping 3 into pentane led to the formation of 4 via a crystal-to-crystyal transformation with the removal of solvent molecules. Complexes 1•+ and 4 were fully characterized by various spectroscopic techniques and single-crystal X-ray analysis. Cation 1•+ features a weak Cr–Co bond with a Wiberg bond order of 0.278. A near-infrared absorption band around 1031 nm was observed for 1•+, which is far red-shifted in comparison to previously reported dinuclear metalloradical species. Complex 4 contains a chromium(II) with a distorted pyramidal geometry and displays single-molecule magnetic properties.
Co-reporter:Li Yang;Jing Li;Tian-Cheng Pu;Ming Kong;Jing Zhang
RSC Advances (2011-Present) 2017 vol. 7(Issue 76) pp:47913-47919
Publication Date(Web):2017/10/11
DOI:10.1039/C7RA08695D
By changing metal ions in the existing [guest][MIIIMII(HCOO)6] framework, heterometallic formate frameworks formulated as [NH2(CH3)2][CrIIIFeII(HCOO)6] (1) and [NH2(CH3)2][CrIIINiII(HCOO)6] (2) were synthesized and characterized by single crystal X-ray diffraction, dielectric measurement and magnetic susceptibility measurement. Both complexes 1 and 2 exhibit long-range ferromagnetic ordering (LRO) at Curie temperatures of 15.3 (1) and 20.9 K (2) through ac magnetization susceptibility and zfc/fc measurements. Complex 1 possesses a hysteresis loop with Hc/Mr being 2.77 kOe/2.83 NμB. Measurements on the dielectric properties of 1 and 2 show an apparent dielectric response. Interestingly, the dielectric constants can be increased under an applied magnetic field.
Co-reporter:Jiancai Liu;Jie Luo;Qing Han;Jing Cao;Lijuan Chen;Junwei Zhao
Journal of Materials Chemistry C 2017 vol. 5(Issue 8) pp:2043-2055
Publication Date(Web):2017/02/23
DOI:10.1039/C6TC05479J
A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.
Co-reporter:Jing Li;Rong-Min Wei;Tian-Cheng Pu;Fan Cao;Li Yang;Yuan Han;Yi-Quan Zhang;Jing-Lin Zuo
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 1) pp:114-122
Publication Date(Web):2017/01/13
DOI:10.1039/C6QI00407E
The magnetic relaxation and magnetization blocking barriers of butterfly complexes, [Dy2Zn2(L)4(NO3)2(CH3OH)2] (1), [Dy2Mn2(L)4(NO3)2(DMF)2] (2) and [Dy2Co2(L)4(NO3)2(DMF)2]·2DMF (3) (H2L = (E)-2-ethoxy-6-(((2-hydroxyphenyl)imino)methyl)phenol), were systematically investigated. The change of SMM behavior originating from the purposeful replacement of two ZnII sites in 1 with MnII and CoII was elucidated by a combined experimental and theoretical study. The quantum tunnelling of magnetization (QTM) was observed in 1. Contrarily, it was quenched in 2 and 3 by spin–spin exchange. A detailed comparative study on these closely-related model complexes reveals the remarkable changes of the ligand field splitting, anisotropy of the Dy-coordinated moiety and the total exchange spectrum due to the replacement of ZnII with CoII and MnII.
Co-reporter:Li Yang;Jing Li;Tian-Cheng Pu;Ming Kong
Dalton Transactions 2017 vol. 46(Issue 20) pp:6670-6676
Publication Date(Web):2017/05/23
DOI:10.1039/C7DT00753A
Three new 3d–3d heterometallic complexes, [CuII3MII(hmb)6(OH)]ClO4·H2O (M = Zn (1), Ni (2) and Co (3)) (Hhmb = 2-hydroxy-3-methoxy-benzaldehyde), have been synthesized. Structural analysis reveals that the three complexes are isostructural. Three CuII ions are in a perfect trigonal geometrical frustration and form a tetrahedral frustrated system with the introduced fourth ion ZnII/NiII/CoII. Magnetic studies indicate the antiferromagnetic coupling between metal ions in all 1, 2 and 3. Due to the geometrical frustration, spin-frustrated magnetism is also a typical feature of 1–3 and the magnetostructural correlation is far more complicated than their structures. The detailed magnetic investigation found that the ground state spin of 2 cannot be simply determined by the antiferromagnetically linear arrangement of spins, because the strong antiferromagnetic coupling between CuII and NiII ions quenches the spin frustration and ferromagnetically polarizes the spins of the [CuII3] unit. Contrarily, the antiferromagnetic coupling between CuII and CoII ions is not strong enough in 3, so there is no similar behaviour compared to 2.
Co-reporter:Dr. Gengwen Tan;Jing Li;Dr. Li Zhang;Chao Chen;Dr. Yue Zhao; Dr. Xinping Wang; Dr. You Song; Dr. Yi-Quan Zhang; Dr. Matthias Driess
Angewandte Chemie International Edition 2017 Volume 56(Issue 41) pp:12741-12745
Publication Date(Web):2017/10/02
DOI:10.1002/anie.201707501
AbstractThe CoII and FeII complexes 1Co and 1Fe with a coordinated phosphorus radical were easily obtained through a charge-transfer approach from the MI precursors LMI(tol) (M=Co, Fe; L=CH(MeC=NDipp)2, Dipp=2,6-iPr2C6H3) to the diazafluorenylidene-substituted phosphaalkene 1. Structural, magnetic, and computational studies on 1Co and 1Fe indicate a weak antiferromagnetic interaction between the high-spin MII ion and the phosphorus radical, resulting in a triplet and quartet ground state, respectively. Complexes 1Co and 1Fe are the first examples of phosphorus-radical-coordinated transition-metal complexes synthesized by charge transfer, providing a new approach to access radicals of heavier main-group elements.
Co-reporter:Lei Chen;JianJun Zhou;Aihua Yuan
Dalton Transactions 2017 vol. 46(Issue 45) pp:15812-15818
Publication Date(Web):2017/11/21
DOI:10.1039/C7DT02905E
Two isostructural mononuclear Dy and Er pentanitrate complexes with an LnO10 coordination geometry have been synthesized and studied by single-crystal X-ray diffraction, luminescence and magnetic measurements. Slow relaxation of the magnetization behavior is simultaneously observed in two complexes with the same coordination environment, despite the different types of the 4f-shell electron distribution. Meanwhile, both complexes exhibit the respective characteristic Ln(III) photoluminescence.
Co-reporter:Fan Cao, Rong-Min Wei, Jing Li, Li Yang, Yuan Han, You Song, and Jian-Min Dou
Inorganic Chemistry 2016 Volume 55(Issue 12) pp:5914-5923
Publication Date(Web):May 26, 2016
DOI:10.1021/acs.inorgchem.6b00255
The mixed 3d–4f pentanuclear complex (Bu4N)[MnIII4YIII(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d–4f–5d hexanuclear complex (Et4N)5[MnIII4YIII(shi)4(OAc)4WV(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d–4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn–N–O]4 connection captures one YIII ion with four bridging acetate anions, completing the eight-coordinated environment around YIII ion, while four methanol molecules each coordinate to the MnIII ions on the other side of the YIII ion. After octacyanotungstate is introduced, the [WV(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between MnIII ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between MnIII ions and the WV ion. Complex 1 [MnIII4YIII] retains an S = 0 ground state, and complex 2 [MnIII4YIIIWV] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four MnIII ions and one WV ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.
Co-reporter:Tuo-Ping Hu, Zhi-Jia Xue, Bao-Hua Zheng, Xiao-Qing Wang, Xue-Na Hao and You Song
CrystEngComm 2016 vol. 18(Issue 28) pp:5386-5392
Publication Date(Web):30 May 2016
DOI:10.1039/C6CE00674D
Two novel metal–organic frameworks, formulated as [Ni3(qptc)2(H2O)3]·3.5H2O·3Me2NH (1) and [Co3(qptc)2(H2O)4]·5H2O (2) (H4qptc = 1,1′:4′,1′′:4′′,1′′′-quaterphenyl-2,4,2′′′,4′′′-tetracarboxylic acid), have been hydrothermally constructed based on a rigid aromatic multicarboxylate ligand. The single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in the triclinic crystal system with space group P and possesses a 4,8-connected 3D open framework including trinuclear nickel Ni3 SBUs, which belongs to an scu topology with the point symbols (416·612) and (44·62). Complex 2 belongs to the monoclinic crystal system with space group C2/c and exhibits a 3D framework containing Co3 SBUs, which is a flu topology with the point symbols (412·612·84) and (46). Furthermore, the variable-temperature magnetic susceptibilities of complexes 1 and 2 have been investigated. Both complexes show weak ferromagnetic coupling between metal ions estimated by using a linear trinuclear model for 1 in the range of 2–300 K and the PHI program for 2 in the range of 20–300 K taking the orbital contribution into consideration.
Co-reporter:Hu Zhou, Qi Chen, Hong-Bo Zhou, Xiao-Zhen Yang, You Song, and Ai-Hua Yuan
Crystal Growth & Design 2016 Volume 16(Issue 3) pp:1708
Publication Date(Web):February 16, 2016
DOI:10.1021/acs.cgd.5b01782
The slow diffusion reaction of octacyanometallate [MoV(CN)8]3–, lanthanide ions (Gd–Lu), and 1,10-phenanthroline (phen) in CH3CN/H2O has yielded eight isostructural one-dimensional chains, [LnIII(phen)2(H2O)MoV(CN)8]2[(n-C4H9)4N](NO3)·2CH3CN·4H2O (Ln = Gd(1), Tb(2), Dy(3), Ho(4), Er(5), Tm(6), Yb(7), Lu(8)), in which [LnIII(phen)2(H2O)]3+ and [MoV(CN)8]3– units are linked alternatively through cyanide groups, generating left- and right-handed helices. Interestingly, 1–8 undergo a resolvation–recrystallization process upon prolonging the diffusion-reaction time, together with the valence change from V to IV of Mo center and structural dimensionalities switching from helical chains to trinuclear clusters, (Hphen)2.5[LnIII0.5(phen)(H2O)][MoIV(CN)8]·1.5CH3CN (Ln = Gd(9), Tb(10), Dy(11), Ho(12), Er(13), Tm(14), Yb(15), Lu(16)). Magnetic studies of 1–16 revealed the typical effects induced by single-ion magnetic anisotropy and/or the population of low-lying excited states, and 11 and 13 showed extraordinary field-induced slow magnetic relaxations.
Co-reporter:Jing Li, Yuan Han, Fan Cao, Rong-Min Wei, Yi-Quan Zhang and You Song
Dalton Transactions 2016 vol. 45(Issue 22) pp:9279-9284
Publication Date(Web):29 Apr 2016
DOI:10.1039/C6DT00979D
A distorted octahedral CoII complex is reported with homoscorpionate ligands. This complex comprised a field-induced single-molecule magnet, showing two slow relaxation processes under a low dc field (<800 Oe) and only one process under a high dc field (≥800 Oe), which was an unusually discovery for 3d metal ions. On the basis of the ac magnetic data, we show for the first time that one of the slow relaxation processes in the low dc field originates from intermolecular dipolar interactions. Interestingly, the Raman process is predominant in the spin reversal relaxation process. The origin of the behaviours of the complex was elucidated by ab initio calculations.
Co-reporter:Zaichao Zhang, Yong Liu, Rong-Min Wei, Zhen-Huan Sheng, Peng Wang, and You Song
Inorganic Chemistry 2015 Volume 54(Issue 23) pp:11049-11051
Publication Date(Web):November 12, 2015
DOI:10.1021/acs.inorgchem.5b01852
[Cu9W6], synthesized by the electrochemical method, may be the ultimate member of the quindecanuclear octacyanometallate-based transition-metal cluster. Its single-crystal structure and magnetic properties were characterized.
Co-reporter:Fei-Lin Yang, Ai-Hua Yuan, Hu Zhou, Hong-Bo Zhou, Dan Yang, You Song, and Yi-Zhi Li
Crystal Growth & Design 2015 Volume 15(Issue 1) pp:176-184
Publication Date(Web):November 26, 2014
DOI:10.1021/cg501128n
Three manganese(II)-octacyanotungstate(V) bimetallic compounds, [Mn(H2O)2(dpe)]3[W(CN)8]2·2dpe·7H2O (dpe = trans-1,2-di(4-pyridyl)ethene) (1), [Mn(H2O)2(azpy)]3[W(CN)8]2·3azpy·4H2O (azpy = 4,4′-azopyridine) (2), and [Mn(H2O)3(azpy)]2[Mn(CH3CN)2(azpy)][W(CN)8]2·5azpy·2H2O (3) were prepared by in situ or secondary assembly methods. Compounds 1 and 2 show three-dimensional (3D) networks through the cross-link of one-dimensional (1D) infinite 3,2-chains or rope-ladder chains with linear ligands (dpe, azpy), while compound 3 adopts a 1D ribbon-like structure by the connection of pentanuclear repeating units with azpy linkers. Magnetic studies reveal that compounds 1–3 show intramolecular antiferromagnetic coupling between Mn(II) and W(V) centers, which produce the typical ferrimagnetic chain behaviors for compounds 1 and 2 but paramagnetic properties for compound 3. Notably, field-induced metamagnetic behavior was detected for compound 2, indicating it undergoes a transition from the antiferromagnetic ground state to ferrimagnetic phase above critical dc field.
Co-reporter:Hua Yang, Fan Cao, Dacheng Li, Suyuan Zeng, You Song and Jianmin Dou
Dalton Transactions 2015 vol. 44(Issue 14) pp:6620-6629
Publication Date(Web):23 Feb 2015
DOI:10.1039/C4DT03822C
An unusual solvent effect on the synthesis of five manganese complexes [Mn2(L1)2(Py)4](1), [Mn2(L1)2(DMSO)4](2), [Mn4(L2)4(OH)4](3), [Mn4(L3)2(DMSO)7(H2O)](4), and [Mn6O2(L4)4(OAc)2(OMe)2(DMSO)4]·MeOH] (5), (H3L1 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid; H2L2 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid amide; H4L3 = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether; and H2L4 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid methyl ester) has been reported. Five complexes have been characterized by X-ray single crystal diffraction, IR, element analysis, thermogravimetric analysis and UV-vis spectra. The analysis reveals that complexes 1 and 2 are isostructural with a bimetallic six-membered ring and L1 from the decomposition of the original H4ppha (H4ppha = 5-(2-hydroxyphenyl)-pyrazole-3-hydroxamic acid) ligand. Complexes 3 and 4 are two tetranuclear clusters, and 3 possesses an aza12-metallacrown-4 core with L2 from the amide functionalization of the decomposition L1; while 4 represents a novel linear [Mn4N8O2] core with L3 from the condensation of L1 and H4ppha. Complex 5 is the first Mn6 cluster linked by two stacked, off-set 8-azametallacrown-3 subunits with [M–N–N–M–N–N–M–O] connectivity, and L4 derived from the esterification of L1. The magnetic behaviour of complexes 1–5 show the dominant antiferromagnetic interactions between metal centers, whereas complex 5 further reveals the coexistence of antiferromagnetic and ferromagnetic interactions, and slow magnetic relaxation at T < 6 K with S = 4 ground state, as well as field induced magnetization saturation.
Co-reporter:Yinfeng Han, You Song
Inorganic Chemistry Communications 2015 Volume 55() pp:83-87
Publication Date(Web):May 2015
DOI:10.1016/j.inoche.2015.03.004
•Seven novel supramolecular compounds based on tetrathiafulvalene tetracarboxylate.•The compounds formed 3D supermolecular frameworks with 1D cationic chains and 1D anionic chains.•1 and 2 shows antiferromagnetic coupling interactions.Seven supramolecular framework, [M(bipy)2(H2O)4][M(TC–TTF)(H2O)2] (M = Mn 1, Co 2, Fe 3, Cu 4, Zn 5 and Cd 6; H4TC–TTF = tetrathiafulvalene tetracarboxylate; bipy = 4,4′-bipyridine) and [Fe4(μ2-Cl)6(OH2)12][H2.5(TC–TTF)]4·4H2O 7 have been prepared by using a diffusion method. 1–6 are isomorphous and crystallize in monoclinic crystal system, space group P21/c (1–5), and C2/m (6), respectively. {[M(TC–TTF)(H2O)2]2 −}n is a 1D polymer anionic chain consisting of MII bridged by TC–TTF4 −. {[M(bipy)2(H2O)4]2 +}n cation forms 1D cationic chain by π···π stacks, and then are linked through O–H···O (N) hydrogen-bonding and π···π interactions to construct a 2D supramolecular net. Furthermore, the 2D nets are connected through O–H···O hydrogen-bonding interactions and form a 3D supramolecular framework. 7 displays a 3D supramolecular framework by O–H···O hydrogen-bonding and S···S interactions with a 1D open channel. Variable–temperature magnetic susceptibility measurements for 1 and 2 show antiferromagnetic coupling interactions at 1.8–300 K.
Co-reporter:Dr. Hua Yang;Dr. Fan Cao; Dacheng Li;Dr. Suyuan Zeng; You Song; Jianmin Dou
Chemistry - A European Journal 2015 Volume 21( Issue 41) pp:14478-14485
Publication Date(Web):
DOI:10.1002/chem.201501644
Abstract
Mixed 3d–4f 12-azametallacrown-4 complexes, [Mn2Ln2(OH)2(hppt)4(OAc)2(DMF)2]⋅2 DMF⋅H2O [Ln=Dy (1), Er (2), Yb (3), Tb (4) and Y (5), H2hppt=3-(2-hydroxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole)], were synthesized by reactions of H2hppt with Mn(OAc)2⋅4 H2O and Ln(NO3)3⋅6 H2O. This is the first 3d–4f azametallacrown family to incorporate Ln ions into the ring sets. These isostructural complexes exhibit alternating arrangements of two Mn and two Ln ions in the rings with each pair of metal centers bound by an NN group and μ2-O bridging. Magnetic measurements revealed dominant antiferromagnetic interactions between metal centers, and frequency-dependent out-of-phase () signals below 4 K suggest slow relaxation of magnetization.
Co-reporter:Lei Chen ; Jing Wang ; Jin-Mei Wei ; Wolfgang Wernsdorfer ; Xue-Tai Chen ; Yi-Quan Zhang ; You Song ;Zi-Ling Xue
Journal of the American Chemical Society 2014 Volume 136(Issue 35) pp:12213-12216
Publication Date(Web):August 13, 2014
DOI:10.1021/ja5051605
The quest for the single-molecular magnets (SMMs) based on mononuclear transition-metal complexes is focused on the low-coordinate species. No transition-metal complex with a coordination number of eight has been shown to exhibit SMM properties. Here the magnetic studies have been carried out for a mononuclear, eight-coordinate cobalt(II)-12-crown-4 (12C4) complex [CoII(12C4)2](I3)2(12C4) (1) with a large axial zero-field splitting. Magnetic measurements show field-induced, slow magnetic relaxation under an applied field of 500 Oe at low temperature. The magnetic relaxation time τ was fitted by the Arrhenius model to afford an energy barrier of Ueff = 17.0 cm–1 and a preexponential factor of τ0 = 1.5 × 10–6 s. The work here presents the first example of the eight-coordinate, mononuclear, 3d metal complex exhibiting the slow magnetic relaxation.
Co-reporter:Ying Chen, Fan Cao, Rong-Min Wei, Yang Zhang, Yi-Quan Zhang and You Song
Dalton Transactions 2014 vol. 43(Issue 9) pp:3783-3791
Publication Date(Web):19 Dec 2013
DOI:10.1039/C3DT53173B
Three ion-pair complexes based on spin-crossover [Mn(5-Br-sal-N-1,5,8,12)]ClO4 with TBA2[Ni(mnt)2], TBA2[Pt(mnt)2] (mnt = maleonitriledithiolate) and TBA[Ni(dmit)2] respectively (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) have been synthesized and structurally characterized. Complexes 1 [Mn(5-Br-sal-N-1,5,8,12)]2[Ni(mnt)2] and 2 [Mn(5-Br-sal-N-1,5,8,12)]2[Pt(mnt)2] are isomorphic and show the axial compression of the octahedral coordination environment of MnIII ions. With the temperature increasing the equatorial metal–ligand bond lengths show significant elongation, but the axial bond lengths remain unchanged. Complex 3 [Mn(5-Br-sal-N-1,5,8,12)][Ni(dmit)2]·CH3CN contains π–π, p–π and H-bonds weak interactions. Magnetic investigation shows the spin-crossover phenomena for 1 and 2, and T1/2 has been increased by 230 K comparing with the reactant complex. However, no spin-crossover was observed in complex 3, and theoretical calculations show that there are weak antiferromagnetic couplings mediated through π–π interactions.
Co-reporter:Ying Chen, Peng-Cheng Mu, Yang Zhang, Xiao-Jiao Song, You Song
Inorganic Chemistry Communications 2014 Volume 47() pp:84-86
Publication Date(Web):September 2014
DOI:10.1016/j.inoche.2014.07.008
•An unpredictable complex {[Cu(terpy)CN]PCQ}n was obtained by in-situ reaction.•{[Cu(terpy)CN]PCQ}n behaves as one-dimensional antiferromagnetic chain.•Cyanide is formed in the process of PCQ− formation from TCNQ−.•This work gives evidence for the formation mechanism of PCQ− from TCNQ−.The in-situ reaction of LiTCNQ (TCNQ = 7,7,8,8-tetracyano-pquinodimethane) and [Cu2(terpy)2(H2O)2(ta)][ClO4]2 (terpy = 2,2′,2″-terpyridine, ta = terephthalate) forms an unpredictable complex {[Cu(terpy)CN]PCQ}n (1) (PCQ = p-tricyanovinylphenyldicyanomethide). X-ray crystallographic analysis and magnetic investigation show that 1 behaves as one-dimensional (1D) antiferromagnetic chains. The production of 1 proves that cyanide is formed in the process of PCQ− formation from TCNQ−.An unpredictable complex {[Cu(terpy)CN]PCQ}n (1) (PCQ = p-tricyanovinylphenyldicyanomethide) was obtained by in-situ reaction. Complex 1 behaves as one-dimensional antiferromagnetic chains, which provides an evidence for the formation of PCQ− from TCNQ−.
Co-reporter:Xi-Yan Dong ; Bo Li ; Bin-Bin Ma ; Shi-Jun Li ; Ming-Ming Dong ; Yan-Yan Zhu ; Shuang-Quan Zang ; You Song ; Hong-Wei Hou ;Thomas. C. W. Mak
Journal of the American Chemical Society 2013 Volume 135(Issue 28) pp:10214-10217
Publication Date(Web):July 5, 2013
DOI:10.1021/ja403449k
A polar homochiral 3D MOF [{Co2(L)(bpe)(H2O)}·5H2O]n constructed with cobalt(II) and a new ligand N-(1,3-dicarboxy-5-benzyl)-carboxymethylglycine (H4L) accommodates ordered helical water streams in its helical grooves. It provides the first example of switchable ferroelectric and optical behavior through two-step reversible single-crystal to single-crystal transformation (SCSC) upon desorption/adsorption of water spirals and coordinated water molecules, respectively.
Co-reporter:Fan Cao, Suna Wang, Dacheng Li, Suyuan Zeng, Meiju Niu, You Song, and Jianmin Dou
Inorganic Chemistry 2013 Volume 52(Issue 19) pp:10747-10755
Publication Date(Web):September 25, 2013
DOI:10.1021/ic3025952
An isomorphous family of mixed 3d–4f dodenuclear aggregates, {[MnIII8Ln4(Clshi)8(OAc)6(μ3-OCH3)2(μ3-O)2(CH3OH)12(H2O)2]·4CH3OH·xH2O)} (where Ln = EuIII (1), GdIII (2), TbIII (3), and DyIII (4); ClshiH3 = 5-chlorosalicylhydroxamic acid; x = 5 for 1 and 3; x = 6 for 2; x = 2 for 4), were synthesized and characterized. They were obtained from the reaction of ClshiH3 with Mn(OAc)2·4H2O and Ln(NO3)3·6H2O. These isomorphous mixed 3d–4f compounds represent a family of novel structures with lanthanide ions in the metallacrown (MC) ring. Each dodecanuclear aggregate contains two offset stacked 14-MC-5 units with M–N–O–M–N–O–Ln–O–N–M–O–N–M connectivity to capture one LnIII ion in the core of each MC. Two 14-MC-5 units are connected through O ions with four Mn ions and six O atoms arranged in a double Mn4O6 cubane. Magnetic measurement indicates that antiferromagnetic interactions are present between the metal ions. The DyIII analogue with high anisotropy and large spin shows slow magnetization relaxation at a direct-current field of 2 kOe.
Co-reporter:Feng Gao, Min-Xia Yao, Yu-Yang Li, Yi-Zhi Li, You Song, and Jing-Lin Zuo
Inorganic Chemistry 2013 Volume 52(Issue 11) pp:6407-6416
Publication Date(Web):May 21, 2013
DOI:10.1021/ic400245n
A series of seven-coordinate mononuclear lanthanide(III) complexes of the general formula [(TPP)Ln(LOEt)]·0.25H2O and [(Pc)Ln(LOEt)] (Ln3+ = Dy3+, Tb3+, Ho3+, and Gd3+; TPP = 5,10,15,20-tetraphenylporphyrinate; Pc = phthalocyaninate; LOEt– = [(η5-C5H5)Co(P(=O)(OEt)2)3]−) are synthesized on the basis of the tripodal ligand LOEt– and either porphyrin or phthalocyanine ligands. All of the complexes are characterized by X-ray crystallography and by static and dynamic magnetic measurements. The Dy and Tb complexes show the field-induced slow relaxation of magnetization, and they are interesting seven-coordinate single-lanthanide-based SMMs. The magnetic relaxation properties of these double-decker sandwich complexes are influenced by the local molecular symmetry and are sensitive to subtle distortions of the coordination geometry of the paramagnetic lanthanide ions, such as metal-to-plane distances, plane center distances, and bending angles.
Co-reporter:Mohd. Muddassir, Xiao-Jiao Song, Ying Chen, Fan Cao, Rong-Min Wei and You Song
CrystEngComm 2013 vol. 15(Issue 48) pp:10541-10549
Publication Date(Web):03 Oct 2013
DOI:10.1039/C3CE41704B
The reaction of trivalent DyIII/HoIII, 2,2′:6′,2′′-terpyridine (terpy), and hexacyanometallate [MIII(CN)6]3− (M = FeIII and CoIII) leads to the formation of a series of cyano-bridged complexes (1–4). In the case of DyIII, one-dimensional (1-D) alternating chains [DyIII(terpy)(DMF)2(H2O)2][MIII(CN)6]·3H2O (M = FeIII for 1 and CoIII for 2) were obtained, where each [MIII(CN)6]3− entity acts as a bis-monodentate bridging ligand towards two DyIII ions through two of its six cyanide groups in cis positions, respectively. Contrarily, in the case of HoIII, a molecular rectangle {[HoIII(terpy)(DMF)(H2O)2][MIII(CN)6]}2·nH2O·2CH3OH {(M = FeIII (3) and CoIII (4); and n = 6 or 7} has been formed although the synthesis method is same as for 1 and 2. Interestingly, solid-state direct-current magnetic susceptibility analyses demonstrate competing ferromagnetic interactions for 1 while complex 3 shows antiferromagnetic interactions. The variable-temperature magnetic behaviours observed for 2 and 4 only originate from isolated Dy and Ho ions, since a diamagnetic CoIII metal ion links the magnetic LnIII ions.
Co-reporter:Xiao-Jiao Song, Mohd. Muddassir, Ying Chen, Hui-Sheng Wang, You Song and Xiao-Zeng You
Dalton Transactions 2013 vol. 42(Issue 4) pp:1116-1121
Publication Date(Web):04 Oct 2012
DOI:10.1039/C2DT31757E
Two heterobimetallic 2-dimensional layer complexes, {[Fe(bpy)(CN)4]2M(4,4′-bipyridine)}·4H2O [bpy = 2,2′-bipyridine, M = Mn (1), Cu (2)] have been prepared by diffusion and their structures determined by single crystal X-ray diffraction. 1 and 2 are isomorphous, made of neutral bimetallic [Fe(bpy)(CN)4]2M(4,4′-bipyridine)] layers and uncoordinated water molecules located between the layers. Interestingly, complex 2 shows the compression of the Jahn–Teller distortion around the copper(II) ion. Magnetic investigation shows antiferromagnetic coupling between the manganese(II) and iron(III) ions mediated by bridging CN− in 1, while ferromagnetic coupling between the copper(II) and iron(III) ions is seen in 2. Both complexes 1 and 2 reveal a metamagnetic-like behaviour with different critical fields (Hc, at 1.8 K): 2.0 kOe (1) and 3.2 kOe (2). The weak interchain antiferromagnetic interaction can be illustrated by the spin-polarization mechanism.
Co-reporter:Xiao-Jiao Song, Zai-Chao Zhang, Yong-Lu Xu, Jun Wang, Hong-Bo Zhou and You Song
Dalton Transactions 2013 vol. 42(Issue 26) pp:9505-9512
Publication Date(Web):12 Apr 2013
DOI:10.1039/C3DT50173F
Reaction of (NBu3H)3[W(CN)8]·H2O and linear trinuclear complexes [CuII2L2LnIII(NO3)3] (L = 2,6-di(acetoacetyl)pyridine, Ln = Eu (1), Gd (2), Tb (3) and Dy (4)) leads to the formation of four one-dimensional (1D) complexes. Single crystal X-ray analysis reveals that [W(CN)8]3− bridges between the [CuII2L2LnIII] sub-building units to construct the alternative chains. Magnetic investigation indicates that ferromagnetic interaction occurred between all paramagnetic ions and the slow magnetic relaxation properties were observed in complexes 3 and 4.
Co-reporter:Hai-Hong Wu, Shuang Yao, Zhi-Ming Zhang, Yang-Guang Li, You Song, Zhu-Jun Liu, Xin-Bao Han and En-Bo Wang
Dalton Transactions 2013 vol. 42(Issue 2) pp:342-346
Publication Date(Web):26 Oct 2012
DOI:10.1039/C2DT32318D
The heterometallic appended {MMnIII4} (M = Dy3+ and K+) cubanes were firstly trapped by two diamagnetic POM shells, which were robust enough to construct inorganic crystalline tubular materials. Magnetic study reveals the presence of a SMM-like slow magnetic relaxation feature in the heterometallic cluster-containing POM.
Co-reporter:Hui-Sheng Wang, You Song
Inorganic Chemistry Communications 2013 Volume 35() pp:86-88
Publication Date(Web):September 2013
DOI:10.1016/j.inoche.2013.05.016
•A cubane-like complex has been obtained from a defect dicubane-like [Ni4] complex in which all end-on or terminal azido ions were replaced by Hhmp multidentate chelating ligands.•This report provides an available way of construction clusters with mixed-chelating ligands.•Overall ferromagnetic coupling between paramagnetic ions within both complexesA defect dicubane-like complex, [Ni4{(2-py)2C(OH)O}2{(2-py)2C(OCH3)O}2 (N3)4]·2CH3CN·2H2O (1) and a cubane-like complex, [Ni4{(2-py)2C(OH)O}3(hmp)3(NO3)].(NO3)·3H2O (2) (Hhmp = 2-hydroxymethylpyridine), were prepared by reacting NiCl2·6H2O with (py)2CO, NaN3 and NMe4OH in MeOH/MeCN and the similar reaction exception the N3− anion replaced by multidentate chelating ligand Hhmp, respectively. X-ray analysis revealed that four Ni2 + ions, four O atoms and two N atoms in 1 were located at the vertices of a defect dicubane; by contrast, four Ni2 + ions and four O atoms in 2 occupied alternate vertices of a [Ni4O4] cubane. Magnetic studies indicated the presence of overall ferromagnetic interactions between Ni2 + ions within both complexes.Two complexes [Ni4{(2-py)2C(OH)O}2{(2-py)2C(OCH3)O}2 (N3)4]·2CH3CN·2H2O (1) and [Ni4{(2-py)2C(OH)O}3(hmp)3(NO3)]·(NO3)·3H2O (2) have been prepared and characterized. While four Ni2 + ions, four O atoms and two N atoms in 1 are located at vertices of a defect dicubane, four Ni2 + ions and four O atoms in 2 occupy alternate vertices of a [Ni4O4].
Co-reporter:Xiao-Jiao Song, Jing-Jing Xu, Ying Chen, Mohd. Muddassir, Fan Cao, Rong-Min Wei, You Song, Xiao-Zeng You
Polyhedron 2013 Volume 66() pp:212-217
Publication Date(Web):13 December 2013
DOI:10.1016/j.poly.2013.04.037
Three cyano-bridged 3d–4f bimetallic rectangular tetranuclear compounds, [FeIII(bpy)(CN)2(μ-CN)2]2[LnIII(NO3)2(H2O)3]2·2H2O·2CH3CN (Ln = Y (1), Tb (2), Dy (3); bpy = 2,2′-bipyridine), have been prepared by diffusion and characterized by single crystal X-ray diffraction, IR spectra, elemental analysis and magnetic measurement. Single-crystal structural analysis shows that 1–3 are isomorphous and made of a neutral tetranuclear unit [FeIII2LnIII2] with two free water and two acetonitrile molecules. Furthermore, the tetranuclear unit [FeIII2LnIII2] is connected into supermolecular three-dimensional framework through hydrogen bonds. Magnetic susceptibility measurements for compounds 1–3 were performed on polycrystalline samples. For compounds 2 and 3, there is weak ferromagnetic interaction between Fe(III) and Ln(III) ions.Three isomorphic cyano-bridged 3d–4f rectangular tetranuclear [FeIII2LnIII2] (Ln = Y, Tb, Dy)] compounds have been prepared and characterized in structurally. The magnetic properties for all compounds have been investigated in details.
Co-reporter:Hu Zhou, Guo-Wang Diao, Su-Yan Qian, Xiao-Zhen Yang, Ai-Hua Yuan, You Song and Yi-Zhi Li
Dalton Transactions 2012 vol. 41(Issue 35) pp:10690-10697
Publication Date(Web):22 Jun 2012
DOI:10.1039/C2DT30615H
The reaction of [W(CN)8]3− with Ln3+ and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H2O)4(pyrazine)0.5W(CN)8 (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(III) and W(V) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks. The magnetic behavior for compounds 1–7 were driven by the lanthanide ions involved. The Ln(III) and W(V) ions in compounds 2 and 5 are ferromagnetically coupled with magnetic ordering occurring at 2.8 K, comparable with magnetic ordering with the critical temperature of 1.9 K for compound 4. In addition, the antiferromagnetic interactions were observed in compounds 3 and 7, while no significant magnetic couplings were found in compounds 1 and 6.
Co-reporter:Xiao-Zhen Yang, Hu Zhou, Su-Yan Qian, Ai-Hua Yuan, Hong-Bo Zhou, You Song
Inorganic Chemistry Communications 2012 Volume 24() pp:40-42
Publication Date(Web):October 2012
DOI:10.1016/j.inoche.2012.07.047
The reaction of Sm3+ ion with [M(CN)8]3− (M = W, Mo) units in the presence of the chelated ligand phen has isolated two octacyanometalate-based assemblies [Sm(phen)(DMF)5][M(CN)8]·CH3OH·H2O (M = Mo, 1; W, 2). Single crystal X-ray diffraction analysis revealed that both compounds are isostructural and the structure consists of Sm3+ centers and [M(CN)8]3− units linked alternatively to generate a one-dimensional (1D) zigzag chain. The chains are further connected together through hydrogen-bonding and π-π stack interactions to form a 3D supramolecular network. The magnetic results revealed that the ferromagnetic interactions were observed between Sm(III) and M(V) centers in both compounds.Two isostructural cyano-bridged Sm(III)M(V) (M = Mo, W) zigzag chains [Sm(phen)(DMF)5][M(CN)8]·CH3OH·H2O (M = Mo, 1; W, 2) with ferromagnetic couplings were prepared in the presence of the aromatic chelated ligand phen.Highlights► Two isostructural cyano-bridged Sm(III)M(V) (M = Mo, W) zigzag chains were isolated using [M(CN)8]3– as building blocks. ► The aromatic chelated ligand phen has played an important role on the formation of low-dimensional systems. ► The ferromagnetic interactions were observed between Sm(III) and M(V) centres.
Co-reporter:Hong-Bo Zhou, Jun Wang, Hui-Sheng Wang, Yong-Lu Xu, Xiao-Jiao Song, You Song, and Xiao-Zeng You
Inorganic Chemistry 2011 Volume 50(Issue 15) pp:6868-6877
Publication Date(Web):June 30, 2011
DOI:10.1021/ic102527h
On the basis of high-spin metal–cyanide clusters of MnIII6MIII (M = Cr, Fe, Co), three one-dimensional (1D) chain complexes, [Mn(salen)]6[Cr(CN)6]2·6CH3OH·H2O (1), [Mn(5-CH3)salen)]6[Fe(CN)6]2·2CH3CN·10H2O (2), and [Mn(5-CH3)salen)]6[Co(CN)6]2·2CH3CN·10H2O (3) [salen = N,N′-ethylenebis(salicylideneiminato) dianion], have been synthesized and characterized structurally as well as magnetically. Complexes 2 and 3 are isomorphic but slightly different from complex 1. All three complexes contain a 1D chain structure which is comprised of alternating high-spin metal–cyanide clusters of [Mn6M]3+ and a bridging group [M(CN)6]3– in the trans mode. Furthermore, the three complexes all exhibit extended 3D supramolecular networks originating from short intermolecular contacts. Magnetic investigation indicates that the coupling mechanisms are intrachain antiferromagnetic interactions for 1 and ferromagnetic interactions for 2, respectively. Complex 3 is a magnetic dilute system due to the diamagnetic nature of CoIII. Further magnetic investigations show that complexes 1 and 2 are dominated by the 3D antiferromagnetic ordering with TN = 7.2 K for 1 and 9.5 K for 2. It is worth noting that the weak frequency-dependent phenomenon of AC susceptibilities was observed in the low-temperature region in both 1 and 2, suggesting the presence of slow magnetic relaxations.
Co-reporter:Suna Wang, Lingqian Kong, Hua Yang, Zhoutong He, Zheng Jiang, Dacheng Li, Suyuan Zeng, Meiju Niu, You Song, and Jianmin Dou
Inorganic Chemistry 2011 Volume 50(Issue 7) pp:2705-2707
Publication Date(Web):March 3, 2011
DOI:10.1021/ic101622d
A novel enneanuclear manganese complex, [Mn9O4(Mesao)6(MeO)3(O2CMe)3(OH)(MeOH)2]·2.5DMF [1; Me-saoH2 = 2-hydroxyphenylethanone oxime], was synthesized. The structure of 1 contains an unusual [Mn9O4] core with an unprecedented defective “supertetrahedron” topology based on two parallel, onset stacked 9-MC-3 and 15-MC-6 metallacrown subunits. Magnetic studies indicate that 1 behaves as a single-molecule magnet.
Co-reporter:Ai-Hua Yuan, Su-Yan Qian, Wen-Yan Liu, Hu Zhou and You Song
Dalton Transactions 2011 vol. 40(Issue 19) pp:5302-5306
Publication Date(Web):05 Apr 2011
DOI:10.1039/C0DT01773F
Reactions of the precursors [Ni(macrocyclic ligand)]2+ with [W(CN)8]3− afford two octacyanotungstate-based assemblies, (H2L1)0.5[Ni(L1)][W(CN)8]·2DMF·H2O (L1 = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) (1) and [Ni(L2)]3[W(CN)8]2·4H2O (L2 = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) (2). Single crystal X-ray diffraction shows that 1 consists of anionic one-dimensional (1D) linear chains, while 2 is built of 2D graphite-like layers with (6, 3) topology. Magnetic studies reveal that both complexes exhibit metamagnetic behavior from the spin-canted antiferromagnet to the ferromagnet induced by field.
Co-reporter:Hong-Bo Zhou, Hui-Sheng Wang, Ying Chen, Yong-Lu Xu, Xiao-Jiao Song, You Song, Yi-Quan Zhang and Xiao-Zeng You
Dalton Transactions 2011 vol. 40(Issue 22) pp:5999-6006
Publication Date(Web):03 May 2011
DOI:10.1039/C0DT01544J
Two hydroxo-bridged complexes, {[MnIII(3-CH3O)salen]2[CrIII(salen)(OH)2]}ClO4·6H2O (1) and {[MnIII(5-CH3)salen]2(OH)}ClO4·3H2O (2) [salen = N,N′-ethylenebis(salicylideneiminato) dianion], have been synthesized by the hydrolysis of the corresponding MnIII(Schiff-Bases) derivatives and [Cr(salen)(H2O)2]Cl precursors. X-Ray structure characterization reveals the discrete linear arched trinuclear structure of 1 and the 1D chain arrangement of 2. Magnetic experimental data and density functional theory (DFT) calculations both indicate the dominant antiferromagnetic interaction mediated by the hydroxo-bridges in both 1 and 2. Frequency-dependent AC susceptibilities reveal slow relaxation of 1 in low temperature. It is worth noting that the structure and magnetic properties of 1 is comparable to a reported cyano-bridged SMM, K[(5-Brsalen)2(H2O)2Mn2Cr(CN)6]·2H2O.
Co-reporter:Subrata Naiya, Hui-Sheng Wang, Michael G. B. Drew, You Song and Ashutosh Ghosh
Dalton Transactions 2011 vol. 40(Issue 12) pp:2744-2756
Publication Date(Web):07 Feb 2011
DOI:10.1039/C0DT00978D
Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(μ-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(μ-NO2)]ClO4 (2b) and [Ni3L′2(μ3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L′ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-μ2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(μ-nitrito-1κO:2κN) bridge is present in addition to the di-μ2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as μ-nitrito-1κO:2κN bridged trinuclear units are linked through a very rare μ3-nitrito-1κO:2κN:3κO′ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of −5.26, −11.45, −10.66 and −5.99 cm−1 for 1, 2a, 2b and 3, respectively.
Co-reporter:Su-Yan Qian, Hu Zhou, Ai-Hua Yuan, and You Song
Crystal Growth & Design 2011 Volume 11(Issue 12) pp:5676-5681
Publication Date(Web):October 11, 2011
DOI:10.1021/cg201217a
The reactions of octacyanometallates [M(CN)8]3- (M = Mo, W) and lanthanide ions Ln3+ (Ln = Pr, Sm, Eu) through the solution diffusion method in the presence of chelated aromatic ligands 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) have yielded five new [M(CN)8]3–-based bimetallic complexes with helical structures: [Ln(phen)2(H2O)Mo(CN)8]2[(n-C4H9)4N](NO3)·2CH3CN·4H2O [Ln = Sm(1), Eu(2)], [Sm(tmphen)2(DMF)2][W(CN)8]·2H2O (3), and [Pr(tmphen)(DMF)5][M(CN)8]·DMF·2H2O [M = Mo(4), W(5)]. The Ln3+ centers are linked alternately by [M(CN)8]3– units through two trans V-shaped cyano groups to form the left- and right-handed helical chains running along the screw axis. Magnetic measurements revealed the presence of an antiferromagnetic interaction between metal centers in 4 and 5.
Co-reporter:Jing-Wei Zhang, Hui-Sheng Wang, You Song
Inorganic Chemistry Communications 2011 Volume 14(Issue 1) pp:56-60
Publication Date(Web):January 2011
DOI:10.1016/j.inoche.2010.09.030
In this research, the synthesis, structure and magnetic properties of an ion-pair complex {[MnII(hmp)2]2(Cl)2}{[MnII(hmp)2WV(CN)8]2} (1) (hmpH = 2-hydroxymethylpyridine) are reported. Complex 1 was prepared by [W (CN)8]3− reacting with Mn(II) salt and hmpH in MeCN solution. Single-crystal X-ray diffraction shows that 1 is crystallized in triclinic system with a space group of P-1 and its structure consists of four parts of two chlorine-bridged [Mn2] cations and two tetrameric [Mn2W2] anionic clusters. The cationic [Mn2] and anionic [Mn2W2] moieties each are connected by π–π stacking to form their own layer. The packing of cations and anions layer by layer via molecular electrostatic potential, Van der Waals force and hydrogen bonding constructs a three-dimensional supramolecular framework. The magnetic analyses show the antiferromagnetic coupling interaction between MnII and WV or MnII and MnII in both parts. No evidence of single-molecule magnet or long-range ordering is observed in the data. By comparing to an analog with spin glass properties, we draw a conclusion that the differences of crystal packing mode, especially the π–π stacking within each layer, could be a key factor for the distinct magnetic properties.Ion-pair complex of {[MnII(hmp)2]2(Cl)2}{[MnII(hmp)2WV(CN)8]2} (hmpH = 2-hydroxymethylpyridine) with square construction was synthesized by [W(CN)8]3− reacting with Mn(II) salt and hmpH in MeCN solution. The magnetic analyses show the antiferromagnetic coupling between metal ions and the influence of π–π stacking on the magnetic properties was investigated.
Co-reporter:KARTIK CHANDRA MONDAL;BAPPADITYA GOLE
Journal of Chemical Sciences 2011 Volume 123( Issue 6) pp:807-818
Publication Date(Web):2011 November
DOI:10.1007/s12039-011-0170-8
An equimolar mixture of Ni(NO3)2·6H2O and pyridine-2-aldehyde with two equivalents of NaN3 in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni2Na2(pic)4(N3)2(H2O)2(MeOH)}· MeOH·3H2O]n (1) and [{Ni2Na2(pic)4(N3)2(H2O)4}·2DMF·H2O]n (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100°C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J ≈ +10 cm − 1 and D ≈ − 2 to −7 cm − 1 for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni\(^{\rm II}_{2}\) dimeric unit, results were J = +20.65 cm − 1 and D = −3.16 cm − 1 for 1, and J = +24.56 cm − 1 and D = −4.67 cm − 1 for 2. However, considering Ni\(^{\rm II}_{2}\)Na\(^{\rm I}_{2}\) cubane as magnetic core the results were J = +16.35 cm − 1 (1), +19.54 cm − 1 (2); D = −3.05 cm − 1 (1), −4.25 cm − 1 (2).
Co-reporter:Hui-Sheng Wang, Xiao-Jiao Song, Hong-Bo Zhou, Ying Chen, Yong-Lu Xu, You Song
Polyhedron 2011 30(18) pp: 3206-3210
Publication Date(Web):
DOI:10.1016/j.poly.2011.04.012
Co-reporter:Hong-Bo Zhou, Zai-Chao Zhang, Ying Chen, You Song, Xiao-Zeng You
Polyhedron 2011 30(18) pp: 3158-3164
Publication Date(Web):
DOI:10.1016/j.poly.2011.03.026
Co-reporter:Jun Wang, Zai-Chao Zhang, Hui-Sheng Wang, Ling-Chen Kang, Hong-Bo Zhou, You Song and Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 7) pp:3101-3103
Publication Date(Web):March 10, 2010
DOI:10.1021/ic100282w
Octacyanotungstate(V) reacts with Cu(NO3)2·2H2O and 1,4,7-trimethyl-1,4,7-triazacyclononane in methanol, resulting in an eicosanuclear cluster [Cu13W7], which shows a diamondoid shape with a Tolkowsky cut and bears intracluster ferromagnetic coupling.
Co-reporter:Dacheng Li ; Huisheng Wang ; Suna Wang ; Yupeng Pan ; Chengjuan Li ; Jianmin Dou
Inorganic Chemistry 2010 Volume 49(Issue 8) pp:3688-3690
Publication Date(Web):March 25, 2010
DOI:10.1021/ic100224j
A tetranuclear manganese complex, [Mn4(hmp)6(N(CN)2)4(H2O)2] [1; Hhmp = 2-(hydroxymethyl)pyridine; N(CN)2− = dicyanamide anion], was synthesized and characterized by single-crystal X-ray diffraction, bond valence sum calculations, IR spectra, elemental analysis, and magnetic measurements. The structure of 1 consists of a linear [MnII2MnIII2] core formed by six hmp− groups linking MnII/III ions. Magnetic studies show that 1 behaves as a single-molecule magnet with ferromagnetic coupling between the metal centers.
Co-reporter:Hu Zhou ; Ai-Hua Yuan ; Su-Yan Qian ; You Song ;Guo-Wang Diao
Inorganic Chemistry 2010 Volume 49(Issue 13) pp:5971-5976
Publication Date(Web):June 9, 2010
DOI:10.1021/ic100518b
The reaction of neutral two-dimensional (2D) layer Tb(H2O)5W(CN)8 with pyrazine in the acetonitrile solution has led to a 3D bimetallic complex, Tb(H2O)4(pyrazine)0.5W(CN)8 (1). In the structure of 1, the eight-coordinated W center adopts a slightly distorted dodecahedron, while the Tb center exhibits a nine-coordinated slightly distorted tricapped trigonal prism. The Tb3+ atoms and the [W(CN)8]3- units are linked in alternating fashion in the ab crystallographic plane, resulting in an infinite 2D corrugated layers. The linear bis-monodentate pyrazine ligands acting as pillars link adjacent layers along the c axis to form an extended 3D open framework. The possible formation mechanism is proposed, and the temperature has played a crucial role for the formation of 1. Magnetic measurements revealed the presence of ferromagnetic interaction between TbIII and WV centers. 1 marks the first structural pattern using the neutral 2D layer as building block and the first 3D complex with LnIII-[WV(CN)]8 found in octacyanometallate-based system. Such a novel and effective building-block methodology will provide a new attractive path forward in developing functionalities of 3D 4f−5d system and may provide an opportunity to obtain 3D magnet in 4f−5d assembly.
Co-reporter:Tian-Wei Wang, Jun Wang, Shin-ichi Ohkoshi, You Song and Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 17) pp:7756-7763
Publication Date(Web):August 2, 2010
DOI:10.1021/ic100591h
A series of three-dimensional (3D) octacyanometallate-based bimetallic magnets, {[Mn(H2O)][Mn0.75(HCOO)0.5(H2O)0.5][W(CN)8]·H2O}4n (1), {[Mn2(HCOO)(HCOOH)][M(CN)8]·H2O}n (M = W (2) and Mo (3)), and {[Mn2(HCOO)(HCOOH)][W(CN)8]·CH3OH}n (M = W (4) and Mo (5)), were synthesized by the reaction of octacyanometallates A3[M(CN)8]·nH2O (A = Na, Cs, and (C4H9)3NH; M = W and Mo; and n = 2 or 4) with manganese salt (Mn(CH3COO)2·4H2O, Mn(ClO4)2·6H2O, and MnCl2·4H2O) in aqueous or methanolic solution containing formic acid. All complexes crystallize in the tetragonal or orthorhombic system. Complex 1 shows an unexpected 3D network structure by connections of manganese ions and octacyanotangstate−manganese double layers via cyanide bridges, while other complexes have typical structure constructions similar to the reported complexes {[MnL]m[M(CN)8]}n (L = CH3COO−, Cl−, and H2O), which the CN group of [WV(CN)8] coordinates to eight MnII ions forming a −[W(CN)8]−Mn4−[W(CN)8]−Mn4− columnar chain, and then all chains share MnII ions as the nodes interlocking with each other to form the 3D networks. Magnetic studies indicate that the cyanide group mediates the antiferromagnetic coupling between octacyanometallates and manganese ions in all complexes, and the ferrimagnetic phase transition temperatures are 53, 52, 42, 49, and 41 K for 1−5, respectively.
Co-reporter:Ling-Chen Kang ; Xin Chen ; Hui-Sheng Wang ; Yi-Zhi Li ; You Song ; Jing-Lin Zuo ;Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9275-9282
Publication Date(Web):September 23, 2010
DOI:10.1021/ic100861n
The reactions of copper(II) salts, 1,3-bis(dimethylamino)-2-propanol (bdmapH) or 1,3-bis(amino)-2-propanol (bapH) and [(Tp)Fe(CN)3]− (Tp = tris(pyrazolyl)hydroborate) gave four mixed-bridged heterometallic one-dimensional (1D) coordination polymers, {[(Tp)2Fe2(CN)6(OAc)(bdmap)Cu2(H2O)]·2H2O}n (1, HOAc = acetic acid), {[(Tp)2Fe2(CN)6(Pa)(bdmap)Cu2(H2O)]·2MeCN}n (2, HPa = propionic acid), {[(Tp)2Fe2(CN)6(Tfa)(bdmap)Cu2(H2O)]·2MeCN}n (3, HTfa = trifluoroacetic acid), and {[(Tp)2Fe2(CN)6(OAc)(bap)Cu2(MeOH)]·2MeOH·H2O}n (4). Complexes 1−3 show unique branched zigzag chain structures and complex 4 exhibits as a steplike chain. Ferromagnetic interactions between FeIII and CuII ions by bridging cyanides are observed in all complexes. Strong antiferromagnetic interactions are presented between the CuII ions in complexes 1−3, whereas similar antiferromagnetic coupling between CuII ions is obviously weakened in complex 4 because of the distortion of penta-coordinated CuII ions.
Co-reporter:Yinfeng Han, Xiaoyan Li, Liqing Li, Chunlin Ma, Zhen Shen, You Song, and Xiaozeng You
Inorganic Chemistry 2010 Volume 49(Issue 23) pp:10781-10787
Publication Date(Web):October 28, 2010
DOI:10.1021/ic902194g
A series of 3-D lanthanide porous coordination polymers, [Ln6(BDC)9(DMF)6(H2O)3·3DMF]n [Ln = La, 1; Ce, 2; Nd, 3], [Ln2(BDC)3(DMF)2(H2O)2]n [Ln = Y, 4; Dy, 5; Eu, 6], [Ln2(ADB)3(DMSO)4·6DMSO·8H2O]n [Ln = Ce, 7; Sm, 8; Eu, 9; Gd, 10], {[Ce3(ADB)3(HADB)3]·30DMSO·29H2O}n (11), and [Ce2(ADB)3(H2O)3]n (12) (H2BDC = benzene-1,4-dicarboxylic acid and H2ADB = 4,4′-azodibenzoic acid), have been synthesized and characterized. In 1−3, the adjacent LnIII ions are intraconnected to form 1-D metal−carboxylate oxygen chain-shaped building units, [Ln4(CO2)12]n, that constructed a 3-D framework with 4 × 7 Å rhombic channels. In 4−6, the dimeric LnIII ions are interlinked to yield scaffolds with 3-D interconnecting tunnels. Compounds 7−10 are all 3-D interpenetrating structures with the CaB6-type topology structure. Compound 11 is constructed by ADB spacers and trinulcear Ce nodes with a NaCl-type topology structure and a 1.9-nm open channel system. In 12, the adjacent CeIII ions are intraconnected to form 1-D metal−carboxylate oxygen chain-shaped building units, [Ln4(CO2)12]n, and give rise to a 3-D framework. Moreover, 6 exhibits characteristic red luminescence properties of EuIII complexes. The magnetic susceptibilities, over a temperature range of 1.8−300 K, of 3, 6, and 7 have also been investigated; the results show paramagnetic properties.
Co-reporter:Ying Wang ; Xi-Li Li ; Tian-Wei Wang ; You Song ;Xiao-Zeng You
Inorganic Chemistry 2010 Volume 49(Issue 3) pp:969-976
Publication Date(Web):December 29, 2009
DOI:10.1021/ic901720a
A series of one-dimensional complexes [Ln(L1)3(HOCH2CH2OH)]n (L1 = 2-furoate anion; Ln = Nd (1), Sm (2), Gd (3), Tb (4), Dy (5), Er (6)) have been synthesized. The complexes were crystallized in the monoclinic space group P2(1)/c and show a chain-like structure determined by single-crystal X-ray diffraction. Magnetic properties indicate that carboxyl group of 2-furoate mediates different magnetic couplings in light and heavy rare earth complexes, namely, antiferromagnetic interaction between light rare earth ions and ferromagnetic interaction between heavy ones. Noticeably, complex 5 displays a strong frequency dependence of alternating current (AC) magnetic properties. Further magnetic studies show a distribution of a single relaxation process in 5. While 1,10-phenanthroline and phthalate anion (L2) were employed, [Dy2(L2)6(H2O)]n (7) was isolated by hydrothermal reactions and characterized magnetically. Research results also show the frequency dependence of AC magnetic susceptibilities, although the phthalate anions mediate antiferromagnetic coupling between DyIII ions. Further magnetic investigation of a neutral mononuclear complex with the formula [Dy(TTA)3(L3)] (8) (TTA = 2-thenoyltrifluoroacetonate; L3 = 4,5-pinene bipyridine) suggests that the single-ion magnetic behavior originates the slow relaxation of DyIII-containing complexes.
Co-reporter:Jun Wang, Youg-Lu Xu, Hong-Bo Zhou, Hui-Sheng Wang, Xiao-Jiao Song, You Song and Xiao-Zeng You
Dalton Transactions 2010 vol. 39(Issue 14) pp:3489-3494
Publication Date(Web):01 Mar 2010
DOI:10.1039/B924203A
The preparation, single-crystal X-ray crystallography and magnetic properties are reported for two tetranuclear cluster complexes based on [WV(CN)8]3− octacyanometallates. Reactions of [WV(CN)8]3− with CoII ions in the presence of the capping ligand tpm (tpm = tri(1H-pyrazol-1-yl)methane) lead to the formation of complex 1 [(tpm)2CoII][WV2(CN)16Co2(tpm)2(H2O)2]·4H2O. Analogous reactions with the MnII produce complex 2 [(tpm)2MnII][WV2(CN)16Mn2(tpm)2(H2O)2]·4H2O. Complexes 1 and 2 are isomorphous and crystallize in the space group of P. Magnetic investigation shows the ferromagnetic coupling between CoII and WV ion in complex 1, while the antiferromagnetic interactions between MnII and WV in complex 2. Further magnetic studies indicate the presence of spin glasses in complex 2, which may be attributed to the further ferromagnetic coupling between anionic and/or cationic cores.
Co-reporter:Ling-Chen Kang, Xin Chen, Xiao-Yu Chen, You Song, Jing-Lin Zuo, Xiao-Zeng You
Inorganic Chemistry Communications 2010 Volume 13(Issue 1) pp:109-111
Publication Date(Web):January 2010
DOI:10.1016/j.inoche.2009.10.032
An unusual μ1,1,3-cyanamido bridged trinuclear copper complex, [(2,2′-bpy)6Cu3(NCN)](ClO4)4·H2O (1) (2,2′-bpy = 2,2′-bipyridine), has been synthesized and structurally characterized. Magnetic studies show the existence of large antiferromagnetic coupling between the copper(II) ions.An unusual μ1,1,3-cyanamido bridged trinuclear copper(II) complex, [(2,2′-bipyridine)6Cu3(NCN)](ClO4)4·H2O, has been prepared and structurally characterized. Magnetic studies show the existence of strong antiferromagnetic coupling.
Co-reporter:Zhi Chen, Bin Zhao, Peng Cheng, Xiao-Qing Zhao, Wei Shi and You Song
Inorganic Chemistry 2009 Volume 48(Issue 8) pp:3493-3495
Publication Date(Web):March 18, 2009
DOI:10.1021/ic801507g
Two lanthanide−organic frameworks, {Ln(TDA)1.5(H2O)2}n [TDA = thiophene-2,5-dicarboxylic acid anion; Ln = Gd (1), Dy (2)], were structurally and magnetically characterized. The magnetic studies revealed that the ferromagnetic coupling existed between adjacent lanthanide ions in 1 and 2, and only 2 displays slow magnetic relaxation behavior with τ0 = 2.4 × 10−8 s and ΔE/kB = 44.2 K. To our knowledge, it is rather rare that ferromagnetic coupling and slow magnetic relaxation coexist in three-dimensional lanthanide-based frameworks.
Co-reporter:Bao-Lin Liu, Hong-Ping Xiao, Emmanuel N. Nfor, You Song, Xiao-Zeng You
Inorganic Chemistry Communications 2009 Volume 12(Issue 1) pp:8-10
Publication Date(Web):January 2009
DOI:10.1016/j.inoche.2008.10.018
A new azido-bridged Mn(II) coordination polymer, [MnL(N3)2]n (1) (L = (E)-3-(dimethylamino)-1-(pyridin-2-yl)prop-2-en-1-one), has been synthesized and characterized by elemental analysis, IR, single crystal X-ray diffraction and magnetic measurement. X-ray analysis shows that complex 1 is a 2D network with (6, 3) layers, in which double end-on (EO) azido-bridged dimers are linked by single end-to-end (EE) azido bridges. Magnetic susceptibilities of 1 were measured under a magnetic field of 2 KOe applied over the temperature range 300–1.8 K. The analysis of magnetic data indicates that the EO- and EE-azido bridges mediate the ferromagnetic and antiferromagnetic exchange interactions, respectively, with the antiferromagnetic coupling between Mn(II) ions dominating the magnetic properties of 1.A new azido-bridged Mn(II) coordination polymer, [MnL(N3)2]n (1), (L = (E)-3-(dimethylamino)-1-(pyridin-2-yl)prop-2-en-1-one), has been synthesized and structurally characterized. Complex 1 shows a 2D (6, 3) structure formed by single EE- and double EO-azido ligands alternately bridging between Mn(II) ions. The magnetic susceptibility was simulated by a model of 1D uniform chain with interchain interaction, giving J = −5.31(3) cm−1 and zJ′ = 4.5(2) cm−1.
Co-reporter:Zhao-Xi Wang, Bao-Lin Liu, Jun Wang, You Song
Inorganic Chemistry Communications 2009 Volume 12(Issue 12) pp:1179-1181
Publication Date(Web):December 2009
DOI:10.1016/j.inoche.2009.09.011
An octacyanotungstate(V)-manganese(II) bimetallic assembly [Mn(Me2-bipy)2]3[W(CN)8]2·9H2O (1) (Me2-bipy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in methanol and characterized by X-ray crystallography. X-ray analysis shows that complex 1 is a neutral, one-dimensional (1D) infinite chain polymer. Magnetic data analysis demonstrates a long-range magnetic interaction and two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions in 1.A new 1D chain octacyanotungstate-manganese complex shows ferrimagnetic behaviour with two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions.
Co-reporter:Ying Wang Dr.;Tian-Wei Wang;Hong-Ping Xiao;Yi-Zhi Li Dr., ;Xiao-Zeng You
Chemistry - A European Journal 2009 Volume 15( Issue 31) pp:7648-7655
Publication Date(Web):
DOI:10.1002/chem.200900578
Abstract
By using cyclohexane-1,2-diamine (chxn), Ni(ClO4)2⋅6H2O and Na3[Mo(CN)8]⋅4H2O, a 3D diamond-like polymer {[NiII(chxn)2]2[MoIV(CN)8]⋅8H2O}n (1) was synthesised, whereas the reaction of chxn and Cu(ClO4)2⋅6H2O with Na3[MV(CN)8]⋅ 4H2O (M=Mo, W) afforded two isomorphous graphite-like complexes {[CuII(chxn)2]3[MoV(CN)8]2⋅2H2O}n (2) and {[CuII(chxn)2]3[WV(CN)8]2⋅2H2O}n (3). When the same synthetic procedure was employed, but replacing Na3[Mo(CN)8]⋅4H2O by (Bu3NH)3[Mo(CN)8]⋅4H2O (Bu3N=tributylamine), {[CuII(chxn)2MoIV(CN)8][CuII(chxn)2]⋅ 2H2O}n (4) was obtained. Single-crystal X-ray diffraction analyses showed that the framework of 4 is similar to 2 and 3, except that a discrete [Cu(chxn)2]2+ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond- or graphite-like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [MoIV(CN)8] bridges mediate very weak antiferromagnetic coupling between the NiII ions in 1, but lead to the paramagnetic behaviour in 4 because [MoIV(CN)8] weakly coordinates to the CuII ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the CuII and WV/MoV ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the WV and CuII ions than between the MoV and CuII ions.
Co-reporter:Zhao-Xi Wang, Xi-Li Li, Bao-Lin Liu, Hiroko Tokoro, Peng Zhang, You Song, Shin-ichi Ohkoshi, Kazuhito Hashimoto and Xiao-Zeng You
Dalton Transactions 2008 (Issue 16) pp:2103-2106
Publication Date(Web):13 Mar 2008
DOI:10.1039/B803273B
Magnetic Cu4 clusters with S = 2 are bridged by octacyanometaltate(IV) to form two 3D cluster arrays of metal–organic frameworks. Magnetic investigation shows the ferromagnetic coupling between Cu(II) ions and very weak antiferromagnetic interaction between clusters.
Co-reporter:Yin-Feng Han, Tian-Wei Wang, You Song, Zhen Shen, Xiao-Zeng You
Inorganic Chemistry Communications 2008 Volume 11(Issue 2) pp:207-210
Publication Date(Web):February 2008
DOI:10.1016/j.inoche.2007.11.020
A new 2D CuII complex [Cu(μ1,1-N3)(tp)(CH3OH)]n (tp = terephthalate) (1) has been synthesized and characterized structurally and magnetically. Single-crystal structural analysis shows that complex 1 consists of 1D CuII chains containing threefold bridging ligands, one μ-1,1-azido, one (syn–syn) terephthalate and one methanol, which are bridged via terephthalate anions to afford a 2D network. Magnetic measurements indicate that complex 1 exhibits intrachain ferromagnetic interaction with J = 63(2) cm−1.A new 2D CuII complex [Cu(μ1,1-N3)(tp)(CH3OH)]n (tp = terephthalate) (1) containing one μ-1,1-azido, one (syn–syn) terephthalate and one methanol bridging ligands, has been synthesized and characterized structurally and magnetically. Magnetic measurements indicate that intrachain ferromagnetic and weak interchain antiferromagnetic coupling exist in complex 1.
Co-reporter:Yin-Feng Han, Min Li, Tian-Wei Wang, Yi-Zhi Li, Zhen Shen, You Song, Xiao-Zeng You
Inorganic Chemistry Communications 2008 Volume 11(Issue 9) pp:945-947
Publication Date(Web):September 2008
DOI:10.1016/j.inoche.2008.04.028
A novel microporous complex [Co2(μ2-OH2)2(H2O)8][H2(TC-TTF)]2 · 2H2O [H4(TC-TTF) = tetra(carboxyl)tetrathiafulvalene] was self-assembled from H4(TC-TTF) and CoCl2 · 6H2O. The complex forms a 3D supramolecular network through hydrogen-bonding and S···S interactions and shows an 1D microporous open channel along the a axis (3.5 × 4.7 Å). Variable-temperature magnetic susceptibility measurement at 1.8–300 K reveals weak ferromagnetic coupling between CoII ions.A novel microporous compound [Co2(μ2-OH2)2(H2O)8][H2(TC-TTF)]2 · 2H2O was self-assembled from the ligand H4(TC-TTF). The compound forms a 3D supramolecular network through hydrogen-bonding and S···S interactions and shows an 1D microporous open channel (3.5 × 4.7 Å). Variable-temperature magnetic susceptibility measurement at 1.8–300 K reveals weak ferromagnetic coupling between CoII ions.
Co-reporter:Xi-Li Li, Bao-Lin Liu, You Song
Inorganic Chemistry Communications 2008 Volume 11(Issue 9) pp:1100-1102
Publication Date(Web):September 2008
DOI:10.1016/j.inoche.2008.06.007
Using chiral bidentate ligand containing N-donors LRR (−)-4,5 pinene bipyridine, a 1D chain single-μ-chloro bridged Cu(II) complex (CuLRRCl2)n (1) was synthesized in methanol and characterized by X-ray crystallography and magnetic measurements. X-ray analysis shows that 1 crystallizes in space group Pbca of orthorhombic. The structure of 1 is a neutral, one-dimensional infinite chain polymer. The magnetic investigations demonstrate that complex 1 exhibits intrachain Cu(II)–Cu(II) antiferromagnetic coupling with J = −2.276 cm−1.A 1D chain single-μ-chloro bridged Cu(II) complex (CuLRRCl2)n (LRR = (−)-4,5 pinene bipyridine) (1) was successfully synthesized and characterized by X-ray crystallography and magnetic measurements. The structure of 1 is a one-dimensional infinite chain polymer, while the magnetic investigations demonstrate that 1 exhibits intrachain Cu(II)–Cu(II) antiferromagnetic interaction with J = −2.276 cm−1.
Co-reporter:Zhao-Xi Wang, Jia Wei, Yi-Zhi Li, Jin-Sheng Guo, You Song
Journal of Molecular Structure 2008 Volume 875(1–3) pp:198-204
Publication Date(Web):17 March 2008
DOI:10.1016/j.molstruc.2007.04.031
Two cyano-bridged trinuclear bimetallic assemblies, [CuII(C8H18N2)2]2[MIV(CN)8]·H2O [M = Mo (1), W (2)], were synthesized by solution of Cu(ClO4)2·6H2O and (+)-cis-1,2,2-trimethyl-1,3-diamino-cyclopentane reacting with K4[Mo(CN)8]·2H2O and Cs3[W(CN)8]·2H2O, respectively. The X-ray crystallography reveals that complexes 1 and 2 are all crystallized in triclinic, P1¯ space group. The single crystal structures of 1 and 2 show each unit cell consists centrosymmetrically of two chiral molecules of Cu2M(CN)8 unit, further leading to the racemization completely. The magnetic investigation exhibits paramagnetic behavior for 1 and very weak antiferromagnetic properties for 2 because the different diamagnetic MIV(CN)8 ion bridges between CuII ions.
Co-reporter:Xi-Li Li;Kai Chen Dr.;Yu Liu Dr.;Zhao-Xi Wang;Tian-Wei Wang;Jing-Lin Zuo Dr.;Yi-Zhi Li Dr.;Yue Wang Dr.;Jin Song Zhu Dr.;Jun-Min Liu Dr. Dr.;Xiao-Zeng You
Angewandte Chemie International Edition 2007 Volume 46(Issue 36) pp:
Publication Date(Web):2 AUG 2007
DOI:10.1002/anie.200701802
Eu-reka! Two neutral mononuclear europium enantiomers [Eu(tta)3L] and their thin films were prepared (tta=2-thenoyltrifluoroacetonate; L=(−)-4,5-pinene bipyridine (1), L=(+)-4,5-pinene bipyridine (2)). The ferroelectric measurements of the thin films show E–P hysteresis loops at room temperature (Tc=28.0 °C) with remnant polarization of 0.022 μC cm−2 and a coercive field of 25 kV cm−1.
Co-reporter:Xi-Li Li;Kai Chen Dr.;Yu Liu Dr.;Zhao-Xi Wang;Tian-Wei Wang;Jing-Lin Zuo Dr.;Yi-Zhi Li Dr.;Yue Wang Dr.;Jin Song Zhu Dr.;Jun-Min Liu Dr. Dr.;Xiao-Zeng You
Angewandte Chemie 2007 Volume 119(Issue 36) pp:
Publication Date(Web):2 AUG 2007
DOI:10.1002/ange.200701802
Beide Enantiomere des einkernigen Europium-Neutralkomplexes [Eu(tta)3L] wurden hergestellt (tta=2-Thenoyltrifluoracetonat; L=(−)- oder (+)-4,5- Pinenbipyridin für 1 bzw. 2). Messungen zum ferroelektrischen Verhalten dünner Filme von 1 und 2 ergaben E-P-Hystereseschleifen bei Raumtemperatur (Tc=28.0 °C) mit einer Restpolarisation von 0.022 μC cm−2 und einem Koerzitivfeld von 25 kV cm−1.
Co-reporter:You Song, Yan Xu, Tian-Wei Wang, Zhao-Xi Wang, Xiao-Zeng You
Journal of Molecular Structure 2006 Volume 796(1–3) pp:36-40
Publication Date(Web):30 August 2006
DOI:10.1016/j.molstruc.2005.12.061
A cyano-bridged mixed-valence CuIICu2I assembly, {CuII(NH3)3CuI(CN)[CuI(CN)3]}n (1), was directly synthesized in diluted ammonia aqueous solution by Cu(NO3)2·3H2O reacting with KCN. The X-ray crystallography displays that complex 1 is crystallized in Monoclinic, P2(1)/n space group with a=9.4680(19), b=12.626(3), c=9.4960(19) Å and β=99.83(3)°. The single crystal structure of complex 1 exhibits 2D network formed by cyanide bridges connecting the ladder chains containing CuII–NC–CuI–NC–CuI–CN–CuII linkage. The magnetic investigation reveals the weak antiferromagnetic interactions between CuII ions in the ladder chain with g=2.138, J∥=−3.39 cm−1 (along the chain) and J⊥=−2.92 cm−1 (perpendicular to the chain) although eight diamagnetic atoms bridging between magnetic center ions. It is suggested due to the largest ionic radius of CuI ion in the first row transition metal ions leading to the diffusion of 3d orbitals of CuI ion, furthermore, the ability of [CuI(CN)3] mediating magnetic interaction is strengthened.
Co-reporter:Zhao-Xi Wang;Xiao-Fei Shen;Jun Wang;Peng Zhang;Yi-Zhi Li;Emmanuel N. Nfor Dr.;Shin-ichi Ohkoshi Dr.;Kazuhito Hashimoto Dr.;Xiao-Zeng You
Angewandte Chemie 2006 Volume 118(Issue 20) pp:
Publication Date(Web):11 APR 2006
DOI:10.1002/ange.200600455
Schwermetallsodalith: NdIII reagiert mit [MoV(CN)8]3− in Methanol zu einem neuen dreidimensionalen Gerüst aus cyanidverbrückten NdIII- und MoIV-Ionen. Das anionische Gerüst (rot und blau im Bild) hat eine ähnliche Käfigstruktur wie der Zeolith Sodalith und enthält hexagonale Kanäle, die mit Methanolmolekülen und [NdIII(H2O)8]3+-Ionen (grüne Kugeln) gefüllt sind.
Co-reporter:Zhao-Xi Wang;Xiao-Fei Shen;Jun Wang;Peng Zhang;Yi-Zhi Li;Emmanuel N. Nfor Dr.;Shin-ichi Ohkoshi Dr.;Kazuhito Hashimoto Dr.;Xiao-Zeng You
Angewandte Chemie International Edition 2006 Volume 45(Issue 20) pp:
Publication Date(Web):11 APR 2006
DOI:10.1002/anie.200600455
Heavy-metal sodalite: NdIII reacts with [MoV(CN)8]3− in methanol to form a new 3D framework consisting of cyanide-bridged NdIII and MoIV ions. The anionic framework (red and blue in the picture) has a cage structure similar to that of the zeolite sodalite and contains hexagonal channels filled by methanol molecules and [NdIII(H2O)8]3+ ions (green spheres).
Co-reporter:Jiancai Liu, Jie Luo, Qing Han, Jing Cao, Lijuan Chen, You Song and Junwei Zhao
Journal of Materials Chemistry A 2017 - vol. 5(Issue 8) pp:NaN2055-2055
Publication Date(Web):2017/01/19
DOI:10.1039/C6TC05479J
A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.
Co-reporter:Jing Li, Rong-Min Wei, Tian-Cheng Pu, Fan Cao, Li Yang, Yuan Han, Yi-Quan Zhang, Jing-Lin Zuo and You Song
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 1) pp:NaN122-122
Publication Date(Web):2016/11/03
DOI:10.1039/C6QI00407E
The magnetic relaxation and magnetization blocking barriers of butterfly complexes, [Dy2Zn2(L)4(NO3)2(CH3OH)2] (1), [Dy2Mn2(L)4(NO3)2(DMF)2] (2) and [Dy2Co2(L)4(NO3)2(DMF)2]·2DMF (3) (H2L = (E)-2-ethoxy-6-(((2-hydroxyphenyl)imino)methyl)phenol), were systematically investigated. The change of SMM behavior originating from the purposeful replacement of two ZnII sites in 1 with MnII and CoII was elucidated by a combined experimental and theoretical study. The quantum tunnelling of magnetization (QTM) was observed in 1. Contrarily, it was quenched in 2 and 3 by spin–spin exchange. A detailed comparative study on these closely-related model complexes reveals the remarkable changes of the ligand field splitting, anisotropy of the Dy-coordinated moiety and the total exchange spectrum due to the replacement of ZnII with CoII and MnII.
Co-reporter:Xiao-Jiao Song, Mohd. Muddassir, Ying Chen, Hui-Sheng Wang, You Song and Xiao-Zeng You
Dalton Transactions 2013 - vol. 42(Issue 4) pp:NaN1121-1121
Publication Date(Web):2012/10/04
DOI:10.1039/C2DT31757E
Two heterobimetallic 2-dimensional layer complexes, {[Fe(bpy)(CN)4]2M(4,4′-bipyridine)}·4H2O [bpy = 2,2′-bipyridine, M = Mn (1), Cu (2)] have been prepared by diffusion and their structures determined by single crystal X-ray diffraction. 1 and 2 are isomorphous, made of neutral bimetallic [Fe(bpy)(CN)4]2M(4,4′-bipyridine)] layers and uncoordinated water molecules located between the layers. Interestingly, complex 2 shows the compression of the Jahn–Teller distortion around the copper(II) ion. Magnetic investigation shows antiferromagnetic coupling between the manganese(II) and iron(III) ions mediated by bridging CN− in 1, while ferromagnetic coupling between the copper(II) and iron(III) ions is seen in 2. Both complexes 1 and 2 reveal a metamagnetic-like behaviour with different critical fields (Hc, at 1.8 K): 2.0 kOe (1) and 3.2 kOe (2). The weak interchain antiferromagnetic interaction can be illustrated by the spin-polarization mechanism.
Co-reporter:Ai-Hua Yuan, Su-Yan Qian, Wen-Yan Liu, Hu Zhou and You Song
Dalton Transactions 2011 - vol. 40(Issue 19) pp:NaN5306-5306
Publication Date(Web):2011/04/05
DOI:10.1039/C0DT01773F
Reactions of the precursors [Ni(macrocyclic ligand)]2+ with [W(CN)8]3− afford two octacyanotungstate-based assemblies, (H2L1)0.5[Ni(L1)][W(CN)8]·2DMF·H2O (L1 = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) (1) and [Ni(L2)]3[W(CN)8]2·4H2O (L2 = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) (2). Single crystal X-ray diffraction shows that 1 consists of anionic one-dimensional (1D) linear chains, while 2 is built of 2D graphite-like layers with (6, 3) topology. Magnetic studies reveal that both complexes exhibit metamagnetic behavior from the spin-canted antiferromagnet to the ferromagnet induced by field.
Co-reporter:Zhao-Xi Wang, Xi-Li Li, Bao-Lin Liu, Hiroko Tokoro, Peng Zhang, You Song, Shin-ichi Ohkoshi, Kazuhito Hashimoto and Xiao-Zeng You
Dalton Transactions 2008(Issue 16) pp:NaN2106-2106
Publication Date(Web):2008/03/13
DOI:10.1039/B803273B
Magnetic Cu4 clusters with S = 2 are bridged by octacyanometaltate(IV) to form two 3D cluster arrays of metal–organic frameworks. Magnetic investigation shows the ferromagnetic coupling between Cu(II) ions and very weak antiferromagnetic interaction between clusters.
Co-reporter:Jun Wang, Youg-Lu Xu, Hong-Bo Zhou, Hui-Sheng Wang, Xiao-Jiao Song, You Song and Xiao-Zeng You
Dalton Transactions 2010 - vol. 39(Issue 14) pp:NaN3494-3494
Publication Date(Web):2010/03/01
DOI:10.1039/B924203A
The preparation, single-crystal X-ray crystallography and magnetic properties are reported for two tetranuclear cluster complexes based on [WV(CN)8]3− octacyanometallates. Reactions of [WV(CN)8]3− with CoII ions in the presence of the capping ligand tpm (tpm = tri(1H-pyrazol-1-yl)methane) lead to the formation of complex 1 [(tpm)2CoII][WV2(CN)16Co2(tpm)2(H2O)2]·4H2O. Analogous reactions with the MnII produce complex 2 [(tpm)2MnII][WV2(CN)16Mn2(tpm)2(H2O)2]·4H2O. Complexes 1 and 2 are isomorphous and crystallize in the space group of P. Magnetic investigation shows the ferromagnetic coupling between CoII and WV ion in complex 1, while the antiferromagnetic interactions between MnII and WV in complex 2. Further magnetic studies indicate the presence of spin glasses in complex 2, which may be attributed to the further ferromagnetic coupling between anionic and/or cationic cores.
Co-reporter:Hong-Bo Zhou, Hui-Sheng Wang, Ying Chen, Yong-Lu Xu, Xiao-Jiao Song, You Song, Yi-Quan Zhang and Xiao-Zeng You
Dalton Transactions 2011 - vol. 40(Issue 22) pp:NaN6006-6006
Publication Date(Web):2011/05/03
DOI:10.1039/C0DT01544J
Two hydroxo-bridged complexes, {[MnIII(3-CH3O)salen]2[CrIII(salen)(OH)2]}ClO4·6H2O (1) and {[MnIII(5-CH3)salen]2(OH)}ClO4·3H2O (2) [salen = N,N′-ethylenebis(salicylideneiminato) dianion], have been synthesized by the hydrolysis of the corresponding MnIII(Schiff-Bases) derivatives and [Cr(salen)(H2O)2]Cl precursors. X-Ray structure characterization reveals the discrete linear arched trinuclear structure of 1 and the 1D chain arrangement of 2. Magnetic experimental data and density functional theory (DFT) calculations both indicate the dominant antiferromagnetic interaction mediated by the hydroxo-bridges in both 1 and 2. Frequency-dependent AC susceptibilities reveal slow relaxation of 1 in low temperature. It is worth noting that the structure and magnetic properties of 1 is comparable to a reported cyano-bridged SMM, K[(5-Brsalen)2(H2O)2Mn2Cr(CN)6]·2H2O.
Co-reporter:Hu Zhou, Guo-Wang Diao, Su-Yan Qian, Xiao-Zhen Yang, Ai-Hua Yuan, You Song and Yi-Zhi Li
Dalton Transactions 2012 - vol. 41(Issue 35) pp:NaN10697-10697
Publication Date(Web):2012/06/22
DOI:10.1039/C2DT30615H
The reaction of [W(CN)8]3− with Ln3+ and pyrazine in acetonitrile yielded a series of isostructural compounds formulated as Ln(H2O)4(pyrazine)0.5W(CN)8 (Ln = La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6), Gd(7)). The Ln(III) and W(V) centers in the structure are linked through cyanide groups to form two-dimensional (2D) layers, which are further pillared by pyrazine, generating 3D frameworks. The magnetic behavior for compounds 1–7 were driven by the lanthanide ions involved. The Ln(III) and W(V) ions in compounds 2 and 5 are ferromagnetically coupled with magnetic ordering occurring at 2.8 K, comparable with magnetic ordering with the critical temperature of 1.9 K for compound 4. In addition, the antiferromagnetic interactions were observed in compounds 3 and 7, while no significant magnetic couplings were found in compounds 1 and 6.
Co-reporter:Subrata Naiya, Hui-Sheng Wang, Michael G. B. Drew, You Song and Ashutosh Ghosh
Dalton Transactions 2011 - vol. 40(Issue 12) pp:NaN2756-2756
Publication Date(Web):2011/02/07
DOI:10.1039/C0DT00978D
Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(μ-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(μ-NO2)]ClO4 (2b) and [Ni3L′2(μ3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L′ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-μ2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(μ-nitrito-1κO:2κN) bridge is present in addition to the di-μ2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as μ-nitrito-1κO:2κN bridged trinuclear units are linked through a very rare μ3-nitrito-1κO:2κN:3κO′ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of −5.26, −11.45, −10.66 and −5.99 cm−1 for 1, 2a, 2b and 3, respectively.
Co-reporter:Hai-Hong Wu, Shuang Yao, Zhi-Ming Zhang, Yang-Guang Li, You Song, Zhu-Jun Liu, Xin-Bao Han and En-Bo Wang
Dalton Transactions 2013 - vol. 42(Issue 2) pp:NaN346-346
Publication Date(Web):2012/10/26
DOI:10.1039/C2DT32318D
The heterometallic appended {MMnIII4} (M = Dy3+ and K+) cubanes were firstly trapped by two diamagnetic POM shells, which were robust enough to construct inorganic crystalline tubular materials. Magnetic study reveals the presence of a SMM-like slow magnetic relaxation feature in the heterometallic cluster-containing POM.
Co-reporter:Xiao-Jiao Song, Zai-Chao Zhang, Yong-Lu Xu, Jun Wang, Hong-Bo Zhou and You Song
Dalton Transactions 2013 - vol. 42(Issue 26) pp:NaN9512-9512
Publication Date(Web):2013/04/12
DOI:10.1039/C3DT50173F
Reaction of (NBu3H)3[W(CN)8]·H2O and linear trinuclear complexes [CuII2L2LnIII(NO3)3] (L = 2,6-di(acetoacetyl)pyridine, Ln = Eu (1), Gd (2), Tb (3) and Dy (4)) leads to the formation of four one-dimensional (1D) complexes. Single crystal X-ray analysis reveals that [W(CN)8]3− bridges between the [CuII2L2LnIII] sub-building units to construct the alternative chains. Magnetic investigation indicates that ferromagnetic interaction occurred between all paramagnetic ions and the slow magnetic relaxation properties were observed in complexes 3 and 4.
Co-reporter:Ying Chen, Fan Cao, Rong-Min Wei, Yang Zhang, Yi-Quan Zhang and You Song
Dalton Transactions 2014 - vol. 43(Issue 9) pp:NaN3791-3791
Publication Date(Web):2013/12/19
DOI:10.1039/C3DT53173B
Three ion-pair complexes based on spin-crossover [Mn(5-Br-sal-N-1,5,8,12)]ClO4 with TBA2[Ni(mnt)2], TBA2[Pt(mnt)2] (mnt = maleonitriledithiolate) and TBA[Ni(dmit)2] respectively (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) have been synthesized and structurally characterized. Complexes 1 [Mn(5-Br-sal-N-1,5,8,12)]2[Ni(mnt)2] and 2 [Mn(5-Br-sal-N-1,5,8,12)]2[Pt(mnt)2] are isomorphic and show the axial compression of the octahedral coordination environment of MnIII ions. With the temperature increasing the equatorial metal–ligand bond lengths show significant elongation, but the axial bond lengths remain unchanged. Complex 3 [Mn(5-Br-sal-N-1,5,8,12)][Ni(dmit)2]·CH3CN contains π–π, p–π and H-bonds weak interactions. Magnetic investigation shows the spin-crossover phenomena for 1 and 2, and T1/2 has been increased by 230 K comparing with the reactant complex. However, no spin-crossover was observed in complex 3, and theoretical calculations show that there are weak antiferromagnetic couplings mediated through π–π interactions.
Co-reporter:Hua Yang, Fan Cao, Dacheng Li, Suyuan Zeng, You Song and Jianmin Dou
Dalton Transactions 2015 - vol. 44(Issue 14) pp:NaN6629-6629
Publication Date(Web):2015/02/23
DOI:10.1039/C4DT03822C
An unusual solvent effect on the synthesis of five manganese complexes [Mn2(L1)2(Py)4](1), [Mn2(L1)2(DMSO)4](2), [Mn4(L2)4(OH)4](3), [Mn4(L3)2(DMSO)7(H2O)](4), and [Mn6O2(L4)4(OAc)2(OMe)2(DMSO)4]·MeOH] (5), (H3L1 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid; H2L2 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid amide; H4L3 = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether; and H2L4 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid methyl ester) has been reported. Five complexes have been characterized by X-ray single crystal diffraction, IR, element analysis, thermogravimetric analysis and UV-vis spectra. The analysis reveals that complexes 1 and 2 are isostructural with a bimetallic six-membered ring and L1 from the decomposition of the original H4ppha (H4ppha = 5-(2-hydroxyphenyl)-pyrazole-3-hydroxamic acid) ligand. Complexes 3 and 4 are two tetranuclear clusters, and 3 possesses an aza12-metallacrown-4 core with L2 from the amide functionalization of the decomposition L1; while 4 represents a novel linear [Mn4N8O2] core with L3 from the condensation of L1 and H4ppha. Complex 5 is the first Mn6 cluster linked by two stacked, off-set 8-azametallacrown-3 subunits with [M–N–N–M–N–N–M–O] connectivity, and L4 derived from the esterification of L1. The magnetic behaviour of complexes 1–5 show the dominant antiferromagnetic interactions between metal centers, whereas complex 5 further reveals the coexistence of antiferromagnetic and ferromagnetic interactions, and slow magnetic relaxation at T < 6 K with S = 4 ground state, as well as field induced magnetization saturation.
Co-reporter:Jing Li, Yuan Han, Fan Cao, Rong-Min Wei, Yi-Quan Zhang and You Song
Dalton Transactions 2016 - vol. 45(Issue 22) pp:NaN9284-9284
Publication Date(Web):2016/04/29
DOI:10.1039/C6DT00979D
A distorted octahedral CoII complex is reported with homoscorpionate ligands. This complex comprised a field-induced single-molecule magnet, showing two slow relaxation processes under a low dc field (<800 Oe) and only one process under a high dc field (≥800 Oe), which was an unusually discovery for 3d metal ions. On the basis of the ac magnetic data, we show for the first time that one of the slow relaxation processes in the low dc field originates from intermolecular dipolar interactions. Interestingly, the Raman process is predominant in the spin reversal relaxation process. The origin of the behaviours of the complex was elucidated by ab initio calculations.
Co-reporter:Rong-Min Wei, Ming Kong, Fan Cao, Jing Li, Tian-Cheng Pu, Li Yang, Xiu-Ling Zhang and You Song
Dalton Transactions 2016 - vol. 45(Issue 46) pp:NaN18652-18652
Publication Date(Web):2016/10/24
DOI:10.1039/C6DT03421G
A series of octacyanotungstate(IV)-based iron(II) complexes with the general formula FeII2(L)8[WIV(CN)8]·nH2O [L = (3-pyridyl)methanol (1, 2), 3-methylpyridine (3), (4-pyridyl)methanol (4), and 4-methylpyridine (5); n = 4 for 1, and n = 0 for 2–5] have been synthesized and characterized. Single crystal X-ray diffraction analysis reveals that the FeII ions lie in the centre of the compressed [FeN6] octahedron in all complexes. FeII and WIV ions are alternately bridged by cyano groups forming a three-dimensional (3D) bimetallic framework. Magnetic investigation shows that 1 displays a gradual spin-crossover (SCO) phenomenon with a spin transition temperature (T1/2) of 200 K, and such SCO behaviour is obviously correlated with the lattice water content of the sample. The magnetic measurements of dehydrated samples show that the fractional conversion from the high-spin (HS) to the low-spin (LS) state is reduced with the increasing of dehydration temperature. Complexes 2–5 are in the HS state and do not exhibit SCO properties in the range of 2–300 K. Comparing the octahedral geometry of [FeN6] of five complexes, quantified by using continuous shape measures, the distortion of complex 1 is the highest as a result of the intermolecular hydrogen bonds, which shorten the Fe–N bond distances and thus increase the ligand field strength at the FeII sites. The analysis of correlations between the structural characteristics and magnetic behaviour of 1–5 suggests that the SCO is mainly tuned by the octahedral distortion of the [FeN6] core caused by intermolecular hydrogen bonds. There is an exact correlation between SCO behaviour and the amount of lattice water molecules existing in the crystal. The spin crossover behaviour of these complexes has been computationally studied using the DFT method. The results of the calculations are consistent with the experiments, which prove that complex 1 with severe distortion of the coordination sphere of FeII is prone to exhibit SCO in theory.
Co-reporter:Hui-Sheng Wang, Feng-Jun Yang, Qiao-Qiao Long, Zhi-Yong Huang, Wei Chen, Zhi-Quan Pan and You Song
Dalton Transactions 2016 - vol. 45(Issue 45) pp:NaN18228-18228
Publication Date(Web):2016/10/11
DOI:10.1039/C6DT02945K
We report the syntheses, crystal structures, and magnetic properties of two 3d–4f heterometallic compounds; namely, [Mn8Ln2O2(OH)2{(py)2CO2}4(teaH)4(CH3COO)6]·6CH3CN·2H2O (LnIII = Dy (1), Tb (2); (py)2CO2H2 = the gem-diol form of di-2-pyridyl ketone, teaH3 = triethanolamine). Both compounds were prepared by the reaction of Mn(OAc)2·4H2O, Ln(NO3)3·5H2O (Ln = Dy and Tb) with the ligands di-2-pyridyl ketone and triethanolamine in MeCN, and they crystallize in the monoclinic space group C2/c. [Mn8Ln2] complexes have not been reported before, and the metallic cores of both complexes were unprecedented. In these cores, two Dy or Tb and two Mn ions comprised a well-known butterfly topology, with three of the remaining six Mn atoms each being situated on either side of the butterfly, linked through two μ3-O2− ions. Six MnIII and two MnII were in six-coordinated distorted octahedrons and two LnIII ions were in nine-coordinated distorted muffins. Interestingly, the coordination sites of LnIII ions are occupied by six O and two N atoms from two teaH2− ligands and one μ3-O2− atom, without the presence of coordinated solvent molecules such as H2O and small anions such as NO3− ions, which is rare in 3d–4f complexes. Remarkably, alternating current (ac) magnetic susceptibility measurements revealed that both complexes displayed dynamic anisotropic magnetic behaviour. The effective energy barrier (Ueff) of complex 2 was estimated to be 18.97 K through high frequency (111–9111 Hz) ac susceptibility measurements. The low symmetry of the coordination configuration of Ln3+ in 1 and 2 may be responsible for the small energy barriers of these two compounds.
Co-reporter:Li Yang, Jing Li, Tian-Cheng Pu, Ming Kong and You Song
Dalton Transactions 2017 - vol. 46(Issue 20) pp:NaN6676-6676
Publication Date(Web):2017/04/20
DOI:10.1039/C7DT00753A
Three new 3d–3d heterometallic complexes, [CuII3MII(hmb)6(OH)]ClO4·H2O (M = Zn (1), Ni (2) and Co (3)) (Hhmb = 2-hydroxy-3-methoxy-benzaldehyde), have been synthesized. Structural analysis reveals that the three complexes are isostructural. Three CuII ions are in a perfect trigonal geometrical frustration and form a tetrahedral frustrated system with the introduced fourth ion ZnII/NiII/CoII. Magnetic studies indicate the antiferromagnetic coupling between metal ions in all 1, 2 and 3. Due to the geometrical frustration, spin-frustrated magnetism is also a typical feature of 1–3 and the magnetostructural correlation is far more complicated than their structures. The detailed magnetic investigation found that the ground state spin of 2 cannot be simply determined by the antiferromagnetically linear arrangement of spins, because the strong antiferromagnetic coupling between CuII and NiII ions quenches the spin frustration and ferromagnetically polarizes the spins of the [CuII3] unit. Contrarily, the antiferromagnetic coupling between CuII and CoII ions is not strong enough in 3, so there is no similar behaviour compared to 2.
![Pyridinium, 1-[(4-iodophenyl)methyl]-, bromide (1:1)](http://img.cochemist.com/ccimg/918200/918145-12-7.png)
![Pyridinium, 1-[(4-iodophenyl)methyl]-, bromide (1:1)](http://img.cochemist.com/ccimg/918200/918145-12-7_b.png)
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![1-[(4-NITROPHENYL)METHYL]QUINOLIN-1-IUM;CHLORIDE](http://img.cochemist.com/ccimg/361200/361148-70-1.png)
![1-[(4-NITROPHENYL)METHYL]QUINOLIN-1-IUM;CHLORIDE](http://img.cochemist.com/ccimg/361200/361148-70-1_b.png)
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![Pyridine, 2,2'-[4-(4-methylphenyl)-4H-1,2,4-triazole-3,5-diyl]bis-](http://img.cochemist.com/ccimg/263600/263568-83-8_b.png)
![1,3-Benzenedicarboxylic acid, 5-[(4-pyridinylcarbonyl)amino]-](/data/chemimg/102900/158520-85-5.png)
![1,3-Benzenedicarboxylic acid, 5-[(4-pyridinylcarbonyl)amino]-](/data/chemimg/102900/158520-85-5_b.png)
![Pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-25,27-diol, 5,11,17,23-tetrakis(1,1-dimethylethyl)-26,28-dimethoxy-](/data/chemimg/371900/122406-45-5.png)
![Pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-25,27-diol, 5,11,17,23-tetrakis(1,1-dimethylethyl)-26,28-dimethoxy-](/data/chemimg/371900/122406-45-5_b.png)
![10H-Phenothiazine, 10,10'-[1,1'-biphenyl]-4,4'-diylbis-](http://img.cochemist.com/ccimg/96900/96817-82-2.png)
![10H-Phenothiazine, 10,10'-[1,1'-biphenyl]-4,4'-diylbis-](http://img.cochemist.com/ccimg/96900/96817-82-2_b.png)
![1-[di(pyrazol-1-yl)methyl]pyrazole](http://img.cochemist.com/ccimg/80600/80510-03-8.png)
![1-[di(pyrazol-1-yl)methyl]pyrazole](http://img.cochemist.com/ccimg/80600/80510-03-8_b.png)
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![Bicyclo[3.1.1]hept-2-ene-2-carboxaldehyde,6,6-dimethyl-, (1S,5R)-](http://img.cochemist.com/ccimg/23800/23727-16-4.png)
![Bicyclo[3.1.1]hept-2-ene-2-carboxaldehyde,6,6-dimethyl-, (1S,5R)-](http://img.cochemist.com/ccimg/23800/23727-16-4_b.png)
![2-Pyridinecarboxylic acid, [(2-hydroxyphenyl)methylene]hydrazide](http://img.cochemist.com/ccimg/15100/15075-87-3.png)
![2-Pyridinecarboxylic acid, [(2-hydroxyphenyl)methylene]hydrazide](http://img.cochemist.com/ccimg/15100/15075-87-3_b.png)
![[hydroxy(pyridin-4-yl)methyl]phosphonic acid](http://img.cochemist.com/ccimg/5500/5422-73-1.png)
![[hydroxy(pyridin-4-yl)methyl]phosphonic acid](http://img.cochemist.com/ccimg/5500/5422-73-1_b.png)
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![Pyridinium, 1-[(4-fluorophenyl)methyl]-, chloride](http://img.cochemist.com/ccimg/473600/473535-50-1_b.png)
![1H-Imidazole, 1,1',1''-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris-](/data/chemimg/133700/220593-43-1.png)
![1H-Imidazole, 1,1',1''-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris-](/data/chemimg/133700/220593-43-1_b.png)
