Gui-lin Zhuang

Magnetic Interaction Affecting the Zero-Field Single-Molecule Magnet Behaviors in Isomorphic {NiII2DyIII2} and {CoII2DyIII2} Tetranuclear Complexes

Co-reporter:Haipeng Wu, Min Li, Sheng Zhang, Hongshan Ke, Yiquan Zhang, Guilin Zhuang, Wenyuan Wang, Qing Wei, Gang Xie, and Sanping Chen

Inorganic Chemistry September 18, 2017 Volume 56(Issue 18) pp:11387-11387

Publication Date(Web):September 6, 2017

DOI:10.1021/acs.inorgchem.7b01840

Great interest is being shown in investigating magnetic interactions that efficiently influence lanthanide single-molecule magnet behavior. A series of heterometallic complexes [M2Ln2(Hhms)2(CH3COO)6(CH3OH)2(H2O)2]·(NO3)2 (M = NiII, Ln = DyIII (1), GdIII (2), and YIII (3); M = CoII, Ln = DyIII (4), GdIII (5), and YIII (6)) have been prepared with a compartmental Schiff-base ligand, 1-(2-hydroxy-3-methoxybenzylidene)-semicarbazide (H2hms), featuring a zigzag-shaped MII-LnIII-LnIII-MII metallic core arrangement. In complexes 1–6, a unique monophenoxo/diacetate asymmetric bridging connects MII ion with LnIII ion, and four acetates bridge two LnIII ions where acetates play essential roles as coligand in generating the tetranuclear units. Magnetic studies reveal the presence of predominant ferromagnetic coupling in DyIII and GdIII derivatives, and slow relaxation of magnetization is observed for {Ni2IIDy2III} and {CoII2DyIII2} with an energy barrier of 16.0 K for {Ni2IIDy2III} and 6.7 K for {CoII2DyIII2} under zero static field. Compared with the analogue {CoII2DyIII2}, the {Ni2IIDy2III} shows longer relaxation time and an absence of the quantum tunnelling of the magnetization (QTM) at low temperatures. Ab initio calculations suggest that the zero-field QTM of {Ni2IIDy2III} is effectively interrupted thanks to the ferromagnetic exchange coupling generated between NiII and DyIII ions. The presence of ferromagnetic exchange between NiII and DyIII ions is more conducive to zero-field single-molecule magnet behaviors than in isomorphic {CoII2DyIII2} where the exchange is antiferromagnetic.

A series of transition metal coordination polymers based on a rigid bi-functional carboxylate–triazolate tecton

Co-reporter:Nan-nan Mao;Peng Hu;Fan Yu;Xi Chen;Tian-le Zhang;Bao Li

CrystEngComm (1999-Present) 2017 vol. 19(Issue 31) pp:4586-4594

Publication Date(Web):2017/08/07

DOI:10.1039/C7CE00808B

By utilizing the pre-designed bi-functional ligand 4-{bis(4-benzoic)amino}-4H-1,2,4-triazole (H2L), five new transition-metal-based coordination polymers, namely, {[Zn(L)]·H2O·DMA}n (1), {[Zn2(L)2]·DMF}n (2),{[Mn(L)]·DMF}n (3), {[Cd(L)]·DMA}n (4) and [Cu3(OH)2(L)2]n (5) have been constructed and structurally characterized. In 1, the tetrahedral zinc ion was incorporated in the final structure. However, complexes 2, 3 and 4 bear 1D Zn-, Mn- and Cd-chains composed of metal ions, triazole and carboxyl groups, respectively. Differently, 1D [Cu4(μ3-OH)2] chains had been stabilized in the 3D structure of 5. In addition, the luminescence or magnetic properties of 1–5 had been correspondingly investigated with the consideration of their crystal structure. The whole research results manifest that utilizing a bi-functional ligand containing carboxyl and triazole groups is an efficient building method in constructing functional CPs.

Insights into Magnetic Interactions in a Monodisperse Gd12Fe14 Metal Cluster

Co-reporter:Xiu-Ying Zheng;Hui Zhang;Dr. Zhenxing Wang;Pengxin Liu;Ming-Hao Du;Ying-Zi Han;Rong-Jia Wei;Zhong-Wen Ouyang; Dr. Xiang-Jian Kong;Dr. Gui-Lin Zhuang; Dr. La-Sheng Long; Dr. Lan-Sun Zheng

Angewandte Chemie 2017 Volume 129(Issue 38) pp:11633-11637

Publication Date(Web):2017/09/11

DOI:10.1002/ange.201705697

AbstractThe largest Ln–Fe metal cluster [Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16(H2O)8]⋅(CH3COO)2(CH3CN)2⋅(H2O)20 (1) and the core–shell monodisperse metal cluster of 1 a@SiO2 (1 a=[Gd12Fe14(μ3-OH)12(μ4-OH)6(μ4-O)12(TEOA)6(CH3COO)16 (H2O)8]2+) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a@SiO2 reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions.

Embedding 1D or 2D cobalt–carboxylate substrates in 3D coordination polymers exhibiting slow magnetic relaxation behaviors: crystal structures, high-field EPR, and magnetic studies

Co-reporter:Nannan Mao;Biquan Zhang;Fan Yu;Xi Chen;Zhenxing Wang;Zhongwen Ouyang;Tianle Zhang;Bao Li

Dalton Transactions 2017 vol. 46(Issue 14) pp:4786-4795

Publication Date(Web):2017/04/05

DOI:10.1039/C7DT00168A

By utilizing well-designed bifunctional ligands derived from 1H-imidazole-4,5-dicarboxylic acid, magnetic coordination polymers (CPs) that exhibit slow magnetic relaxation at the low temperature regions were constructed and further structurally characterized. In 1, 1D cobalt–carboxyl chains were stabilized in the final structure. In contrast, by adjusting the length of the substituted arms on imidazole-4,5-dicarboxylic acid, a novel 3D CP, 2 containing 2D 63 cobalt–carboxyl layer was obtained. A combination of Quantum Monte Carlo (QMC) simulations and the first-principles Density functional theory (DFT) calculations showed that compound 2 features weak ferro- and antiferro-magnetic coupling mechanisms with two different super-exchange paths of −/+/− for syn–anti carboxylate bridges and −/−/− for syn–syn carboxylate bridges. Through HF-EPR measurements performed on polycrystalline samples over the frequency range of 60–260 GHz and field range of 0–12 T, the effective g-values of 1 and 2 were all larger than 2.00, and the signs of their D values were probably positive.

Ionothermal synthesis, magnetic transformation and hydration–dehydration properties of Co(II)-based coordination polymers

Co-reporter:Wen-Xian Chen, Yi-Fen Gao, Pei-Yuan Gao, Qiu-Ping Liu and Gui-Lin Zhuang

RSC Advances 2016 vol. 6(Issue 76) pp:71952-71957

Publication Date(Web):22 Jul 2016

DOI:10.1039/C6RA14268K

Two low-coordinated coordination polymers, [Co(nip)2][EMIm]2 (1) (H2nip = 5-nitryl-isophthalic acid, EMIm = 1-ethyl-3-methyl imidazolium) and [Co(bptc)][EMIm]2·H2O (2) (H4bptc = 2,2′,4,4′-biphenyltetracarboxylic acid) were prepared under an ionic liquid medium, demonstrating that ionothermal synthesis may act as a powerful tool in the preparation of low-coordinated coordination polymers (LCCPs). Investigation on the synthetic conditions shows that a lower reaction temperature, appropriate ratio of ligand to metal ions, and hydrophobic ionic liquid are of key importance for the formation of LCCPs. Both of them feature interesting hydration–dehydration properties with reversible color changing from deep purple to pink. Solid state UV-Vis spectra measurements also indicate that the largest adsorbtion peaks are blue-shifted under hydration. Significantly, under hydration and dehydration processes, compound 2 exhibits a magnetic transformation from anti-ferromagnetism to ferrimagnetism. Essentially, this transformation arises from the formation of new propagating ways triggered by guest water.

Magnetic Properties of a Single-Molecule LanthanideTransition-Metal Compound Containing 52 Gadolinium and 56 Nickel Atoms

Co-reporter:Da-Peng Liu;Xin-Ping Lin;Hui Zhang;Xiu-Ying Zheng;Dr. Gui-Lin Zhuang;Dr. Xiang-Jian Kong;Dr. La-Sheng Long;Dr. Lan-Sun Zheng

Angewandte Chemie 2016 Volume 128( Issue 14) pp:4608-4612

Publication Date(Web):

DOI:10.1002/ange.201601199

Abstract

Monodisperse metal clusters provide a unique platform for investigating magnetic exchange within molecular magnets. Herein, the core–shell structure of the monodisperse molecule magnet of [Gd₅₂Ni₅₆(IDA)₄₈(OH)₁₅₄(H₂O)₃₈]@SiO₂ (1 a@SiO₂) was prepared by encapsulating one high-nuclearity lanthanide–transition-metal compound of [Gd₅₂Ni₅₆(IDA)₄₈(OH)₁₅₄(H₂O)₃₈]⋅(NO₃)₁₈⋅164 H₂O (1) (IDA=iminodiacetate) into one silica nanosphere through a facile one-pot microemulsion method. 1 a@SiO₂ was characterized using transmission electron microscopy, N₂ adsorption–desorption isotherms, and inductively coupled plasma-atomic emission spectrometry. Magnetic investigation of 1 and 1 a revealed J₁=0.25 cm⁻¹, J₂=−0.060 cm⁻¹, J₃=−0.22 cm⁻¹, J₄=−8.63 cm⁻¹, g=1.95, and z J=−2.0×10⁻³ cm⁻¹ for 1, and J₁=0.26 cm⁻¹, J₂=−0.065 cm⁻¹, J₃=−0.23 cm⁻¹, J₄=−8.40 cm⁻¹ g=1.99, and z J=0.000 cm⁻¹ for 1 a@SiO₂. The z J=0 in 1 a@SiO₂ suggests that weak antiferromagnetic coupling between the compounds is shielded by silica nanospheres.

Magnetic Properties of a Single-Molecule LanthanideTransition-Metal Compound Containing 52 Gadolinium and 56 Nickel Atoms

Co-reporter:Da-Peng Liu;Xin-Ping Lin;Hui Zhang;Xiu-Ying Zheng;Dr. Gui-Lin Zhuang;Dr. Xiang-Jian Kong;Dr. La-Sheng Long;Dr. Lan-Sun Zheng

Angewandte Chemie International Edition 2016 Volume 55( Issue 14) pp:4532-4536

Publication Date(Web):

DOI:10.1002/anie.201601199

Abstract

Monodisperse metal clusters provide a unique platform for investigating magnetic exchange within molecular magnets. Herein, the core–shell structure of the monodisperse molecule magnet of [Gd₅₂Ni₅₆(IDA)₄₈(OH)₁₅₄(H₂O)₃₈]@SiO₂ (1 a@SiO₂) was prepared by encapsulating one high-nuclearity lanthanide–transition-metal compound of [Gd₅₂Ni₅₆(IDA)₄₈(OH)₁₅₄(H₂O)₃₈]⋅(NO₃)₁₈⋅164 H₂O (1) (IDA=iminodiacetate) into one silica nanosphere through a facile one-pot microemulsion method. 1 a@SiO₂ was characterized using transmission electron microscopy, N₂ adsorption–desorption isotherms, and inductively coupled plasma-atomic emission spectrometry. Magnetic investigation of 1 and 1 a revealed J₁=0.25 cm⁻¹, J₂=−0.060 cm⁻¹, J₃=−0.22 cm⁻¹, J₄=−8.63 cm⁻¹, g=1.95, and z J=−2.0×10⁻³ cm⁻¹ for 1, and J₁=0.26 cm⁻¹, J₂=−0.065 cm⁻¹, J₃=−0.23 cm⁻¹, J₄=−8.40 cm⁻¹ g=1.99, and z J=0.000 cm⁻¹ for 1 a@SiO₂. The z J=0 in 1 a@SiO₂ suggests that weak antiferromagnetic coupling between the compounds is shielded by silica nanospheres.

Lanthanide-based metal–peptide frameworks prepared by ionothermal method: Anion direct effect, DFT calculation and luminescence property

Co-reporter:Wen-xian Chen, Li Tan, Qiu-ping Liu, Ying Zhou, Yong-xian Fan, Gen-rong Qiang, Gui-lin Zhuang

Inorganic Chemistry Communications 2014 Volume 42() pp:29-32

Publication Date(Web):April 2014

DOI:10.1016/j.inoche.2014.01.014

•Four new lanthanide-based MPFs were obtained by ionothermal method.•DFT calculation reveals that bromine ions play an important role in their structure.•Luminescence analysis shows that 3 and 4 behave good fluorescence properties.A series of new isomorphic lanthanide-based metal–peptide frameworks, [Ln(PODC)(H2O)2]Br (Ln = La(1), Nd(2), Eu(3), Tb(4), H2PODC = 2, 5-piperazinedione-1, 4-diacetic acid), were synthesized under the ionic liquid medium. Crystal structure measure results exhibit that they are new three-dimensional frameworks, where bromine anions of ionic liquid are enveloped in the pore. Interestingly, it is found that bromine anions can effectively counteract the effects of lanthanide ions (e.g. lanthanide contraction). Via the first-principles DFT calculation, it is obtained that bromine anions of ion liquid influence the electronic properties of PODC2 − ligand and thereby directly control the structure. Luminescence analysis demonstrates that compounds 3 and 4 have good fluorescence properties, where the emission peaks can be ascribed to the transitions of 5D0 → 7FJ (J = 0, 1, 2, 3, 4) for 3 and 5D4 → 7FJ (J = 6, 5, 4, 3) for 4.Four lanthanide-based metal–peptide frameworks under ionothermal condition exhibit new three-dimensional framework and further reveal that anion of ion liquid plays an important role in structure by DFT calculation.

The effect of earth metal ion on the property of peptide-based metal–organic frameworks

Co-reporter:Wu-lin Chen, Wen-Xian Chen, Gui-lin Zhuang, Jun Zheng, Li Tan, Xing Zhong and Jian-guo Wang

CrystEngComm 2013 vol. 15(Issue 27) pp:5545-5551

Publication Date(Web):09 May 2013

DOI:10.1039/C3CE40587G

A series of alkaline earth metal-based bio-analogous metal–organic frameworks (1–4) based on a cyclic dipeptide (2,5-piperazinedione-1,4-diacetic acid, H2PODC) were prepared under the same synthetic conditions and the effect of earth metal ion on the (geometrical and electronic) property of these MOFs was investigated. Crystal analysis demonstrates that the metal ion radii play an important role in coordination number, coordination modes of the ligand and bond length. The binding mode between metal ion and peptide can be divided into two groups: (1) Mg2+ and Sr2+; (2) Ca2+ and Ba2+ ions, where the difference is whether the carbonyl group participates in coordination. The result may be relevant to the different biophysical phenomena of protein between alkaline earth metal ions. UV-vis spectra show two adsorption peaks for compounds 1–4, while fluorescence spectra display one emission peak. Via first-principles density functional theory (DFT) calculation, we found that two adsorption peaks should be attributed to the transition of valence band (VB) → two empty bands and VB → conduction band (CB), while one emission peak may result from the transition of CB → VB.

Hybrid nanotube–graphene junctions: spin degeneracy breaking and tunable electronic structure

Co-reporter:Zhi-bei Qu, Li Gu, Meina Li, Guoyue Shi and Gui-lin Zhuang

Physical Chemistry Chemical Physics 2013 vol. 15(Issue 46) pp:20281-20287

Publication Date(Web):02 Oct 2013

DOI:10.1039/C3CP53295J

Hybrid carbon nanostructures have attracted enormous interest due to their structural stability and unique physical properties. Geometric and physical properties of a carbon nanotube (CNT)–graphene nanoribbon (GNR) hybrid system were investigated via first-principles density functional theory (DFT) calculations. The nanotube–graphene junction (NTGJ), where the GNR directly links to the CNT by covalent bonds, shows novel electronic dependence on the structural parameters of the building-blocks, such as chirality, nanotube diameter and width of the nanoribbon. For an armchair NTGJ, a small band gap opens up representing asymmetrical spin-up and spin-down bands. However, zig-zag NTGJ shows direct semi-conducting characteristics with a tunable band gap ranging from zero to 0.6 eV. Interestingly, the value of the band gap follows the specific width and diameter dependent oscillations, namely the 3p − 1 principle. Transition-state results reveal the formation of NTGJs is exothermic and has a low energy-barrier. In addition, nanotube–graphene–nanotube junctions or namely dumbbell NTGJs were also studied, which exhibits similar properties with single NTGJ.

Position of substituent dependent dimensionality in Ln–Cu heterometallic coordination polymers

Co-reporter:Gui-lin Zhuang, Wen-xian Chen, Gan-ning Zeng, Jian-guo Wang and Wu-lin Chen

CrystEngComm 2012 vol. 14(Issue 2) pp:679-683

Publication Date(Web):09 Nov 2011

DOI:10.1039/C1CE05864A

The reaction of two derivatives of iminodiacetic acid, including H2ANMA (H2ANMA = L-alanine-N-monoacetic acid) and H2MIDA (H2MIDA = N-methyl-iminodiacetic acid), with Ln(NO3)3 (Ln = La, Pr, Nd) and Cu(NO3)2 generates two types of Ln–Cu coordination polymers of different dimensionality, {[Ln2Cu3(ANMA)6](H2O)3} and {[Ln2Cu(MIDA)4(H2O)6](H2O)4} (Ln = La, Pr, Nd). Crystal structure analysis reveals that the position of the methyl group in the two ligands plays an important role, which can be described as follows: (1) adjusting the coordination direction of ligand via the steric hindrance; (2) serving as an electron donating group to enhance the coordination ability of the amino group, where the H2MIDA ligand displays a new coordination mode. It is found that the position of the methyl groups in the two ligands plays a critical role in their structural differences.

Synthesis, magnetism and quantum Monte Carlo studies of two Cu(II)-based ferromagnetic coordination polymers

Co-reporter:Gui-lin Zhuang, Wen-xian Chen, Jun Zheng, Wu-lin Chen, Jian-guo Wang

Inorganic Chemistry Communications 2012 Volume 22() pp:18-21

Publication Date(Web):August 2012

DOI:10.1016/j.inoche.2012.05.004

Two Cu(II)-based coordination polymers, {Cu(CMBA)(H2O)}n (1) and {Cu(CMBA)(4, 4′-bpy)0.5(H2O)}n (2) (H2CMBA = 2-(Carboxymethyl-amino)-3-methyl-butyric acid, 4, 4′-bpy = 4, 4′-bipyridine), were obtained under microwave irradiation. Magnetic property measurements indicate that both of them feature ferromagnetic characteristic. Furthermore, quantum Monte Carlo studies respectively reveal that the coupling parameters between the adjacent Cu(II) ions are 8.20 cm− 1 for 1 and 3.60 cm− 1 for 2, respectively. Moreover, it is found that 4, 4′-bpy ligand serves as a weak antiferromagnetic propagation pathway with − 0.36 cm− 1 between two adjacent Cu(II) chains in 2, resulting in the differences of magnetization between 1 and 2.Two Cu(II)-based coordination polymers prepared under microwave irradiation reveal ferromagnetic propagation of 8.20 cm− 1 for 1 and 3.60 cm− 1 for 2 by quantum Monte Carlo method.Highlights► Two Cu(II) based coordination polymers of H2CMBA ligand were obtained. ► Magnetic measure exhibits that they feature ferromagnetic properties. ► Quantum Monte Carlo studies reveal the coupling parameters of two Cu(II) ions. ► 4, 4′-bpy ligand exhibits weak antiferromagnetic interaction with − 0.36 cm− 1.

Embedding 1D or 2D cobalt–carboxylate substrates in 3D coordination polymers exhibiting slow magnetic relaxation behaviors: crystal structures, high-field EPR, and magnetic studies

Co-reporter:Nannan Mao, Biquan Zhang, Fan Yu, Xi Chen, Gui-lin Zhuang, Zhenxing Wang, Zhongwen Ouyang, Tianle Zhang and Bao Li

Dalton Transactions 2017 - vol. 46(Issue 14) pp:NaN4795-4795

Publication Date(Web):2017/03/13

DOI:10.1039/C7DT00168A

By utilizing well-designed bifunctional ligands derived from 1H-imidazole-4,5-dicarboxylic acid, magnetic coordination polymers (CPs) that exhibit slow magnetic relaxation at the low temperature regions were constructed and further structurally characterized. In 1, 1D cobalt–carboxyl chains were stabilized in the final structure. In contrast, by adjusting the length of the substituted arms on imidazole-4,5-dicarboxylic acid, a novel 3D CP, 2 containing 2D 63 cobalt–carboxyl layer was obtained. A combination of Quantum Monte Carlo (QMC) simulations and the first-principles Density functional theory (DFT) calculations showed that compound 2 features weak ferro- and antiferro-magnetic coupling mechanisms with two different super-exchange paths of −/+/− for syn–anti carboxylate bridges and −/−/− for syn–syn carboxylate bridges. Through HF-EPR measurements performed on polycrystalline samples over the frequency range of 60–260 GHz and field range of 0–12 T, the effective g-values of 1 and 2 were all larger than 2.00, and the signs of their D values were probably positive.

Hybrid nanotube–graphene junctions: spin degeneracy breaking and tunable electronic structure

Co-reporter:Zhi-bei Qu, Li Gu, Meina Li, Guoyue Shi and Gui-lin Zhuang

Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 46) pp:NaN20287-20287

Publication Date(Web):2013/10/02

DOI:10.1039/C3CP53295J

Hybrid carbon nanostructures have attracted enormous interest due to their structural stability and unique physical properties. Geometric and physical properties of a carbon nanotube (CNT)–graphene nanoribbon (GNR) hybrid system were investigated via first-principles density functional theory (DFT) calculations. The nanotube–graphene junction (NTGJ), where the GNR directly links to the CNT by covalent bonds, shows novel electronic dependence on the structural parameters of the building-blocks, such as chirality, nanotube diameter and width of the nanoribbon. For an armchair NTGJ, a small band gap opens up representing asymmetrical spin-up and spin-down bands. However, zig-zag NTGJ shows direct semi-conducting characteristics with a tunable band gap ranging from zero to 0.6 eV. Interestingly, the value of the band gap follows the specific width and diameter dependent oscillations, namely the 3p − 1 principle. Transition-state results reveal the formation of NTGJs is exothermic and has a low energy-barrier. In addition, nanotube–graphene–nanotube junctions or namely dumbbell NTGJs were also studied, which exhibits similar properties with single NTGJ.

The ionothermal synthesis, structure, and magnetism–structure relationship of two biphenyl tetracarboxylic acid-based metal–organic frameworks

Co-reporter:Wen-Xian Chen, Li Tan, Qiu-Ping Liu, Gen-Rong Qiang and Gui-Lin Zhuang

Dalton Transactions 2014 - vol. 43(Issue 43) pp:NaN16521-16521

Publication Date(Web):2014/09/02

DOI:10.1039/C4DT02042A

Two new metal–organic frameworks (1–2) were ionothermally obtained by the reaction of a biphenyltetracarboxylic sodium (Na4BPTC) ligand and M(OOCCH3)2 (M = Co(1) and Mn(2)). Crystal structure analysis reveals that 1 is a Co3Na6 unit-based three dimensional heterometallic MOF, while 2 exhibits a {Mn(COO)n} chain-based three-dimensional framework. Furthermore, the magnetic measurement shows that both of them have anti-ferromagnetic properties. A combination of Density Functional Theory (DFT) and Quantum Monte Carlo (QMC) simulation uncovers that in 2 the coupling parameters between two adjacent Mn(II) ions are J1 = −2.0 cm−1 and J2 = −1.6 cm−1, and the magnetism mainly originates from the propagation of Mn(II) ions by the super-exchange of carboxylates. Interestingly, the superexchange modes of J1 and J2 are different. Two spin nets of −/+/− dominate in the coupling for J1, while for J2 there are two spin nets of −/+/− and one spin net of +/−/+.

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Abstract

Abstract