Co-reporter:Yan-Yuan Jia, Xiao-Ting Liu, Rui Feng, Shi-Yu Zhang, Ping Zhang, Ya-Bing He, Ying-Hui Zhang, and Xian-He Bu
Crystal Growth & Design May 3, 2017 Volume 17(Issue 5) pp:2584-2584
Publication Date(Web):April 7, 2017
DOI:10.1021/acs.cgd.7b00119
In order to elucidate the effect of the structure on stability and gas adsorption performance, three porous Zn(II) metal–organic frameworks, NKU-106, NKU-107, and NKU-108, have been constructed. NKU-106 and NKU-107 assembled from acylamide functionalized tetracarboxylate ligand exhibit low stability and thereby poor gas adsorption ability. However, when one isophthalate moiety of the tetracarboxylate ligand is replaced with a pyrazole group, and the resulting NKU-108 shows improved thermal and chemical stability as well as good adsorption capacities with respect to CO2 and C2 hydrocarbons. This result demonstrates that coordination group optimization is an effective strategy to improve the stability and gas adsorption properties of metal–organic frameworks (MOFs) and thus provides very valuable information for future design and synthesis of porous MOFs for practical application.
Co-reporter:Ming Zhong;Dong-Hui Yang;Ling-Jun Kong;Wei Shuang;Xian-He Bu
Dalton Transactions 2017 vol. 46(Issue 45) pp:15947-15953
Publication Date(Web):2017/11/21
DOI:10.1039/C7DT03047A
Developing high-performance electrode materials to replace a traditional graphite electrode is critical for the commercialization of lithium ion batteries, which however still remains a great challenge. Herein, we report a suitable method to synthesize a series of well-dispersed nanostructured Co3O4–CoFe2O4 composites (CCFs) from bimetallic metal–organic frameworks (BiMOFs) with varied Fe3+/Co2+ molar ratios. When used as anodes for lithium ion batteries, the CCF-12 composite exhibits a maximum initial discharge capacity of 1328 mA h g−1, a reversible capacity of 940 mA h g−1 at 100 mA g−1 after 80 cycles, and a better rate capability in comparison with those of pure Co3O4 and other CCF composites. The well-dispersed structure and small particle size are believed to mainly contribute to the outstanding electrochemical performance of CCF-12 electrodes.
Co-reporter:
Journal of Polymer Science Part A: Polymer Chemistry 2017 Volume 55(Issue 8) pp:1329-1337
Publication Date(Web):2017/04/15
DOI:10.1002/pola.28500
ABSTRACTSeveral hollow porous organic polymers were conveniently fabricated by poly-condensation of tetraphenyl porphyrin (TPP), tetrabiphenyl porphyrin (TBPP), or triphenylbenzene (TPB), with nano-sized ZnO particles as template and AlCl3 as catalyst. The hollow polymers exhibit much enhanced adsorption capacity for organic dyes in aqueous solution relative to the pristine polymers. Particularly, the hollow polymer based on TBPP (h-COP-P) displays high adsorption capacity (460 mg/g within 500 min) as well as good recycling performance toward Rhodamine B. This capacity is about three times larger than that of corresponding pristine POPs (COP-P) and is even comparable with the best performed organic polymers reports to date, which is ascribed to its unique hydrophobic hollow structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1329–1337
Co-reporter:Yan-Yuan Jia, Guo-Jian Ren, Ai-Lin Li, Li-Zhu Zhang, Rui Feng, Ying-Hui Zhang, and Xian-He Bu
Crystal Growth & Design 2016 Volume 16(Issue 10) pp:5593
Publication Date(Web):September 19, 2016
DOI:10.1021/acs.cgd.6b00813
In this paper, two 3D anionic metal–organic frameworks, [(CH3CH2)2NH2]·[Zn(BTC)1/3(PyC)]·1/2CH3CN·2H2O (NKU-102) and [(CH3CH2)2NH2]·[Zn2(BTC) (PyC)]·1.5H2O·DEF (NKU-103), were constructed from the same reaction system at different temperature. Though both are of anionic framework, NKU-102 possesses a sealed 3D framework based on octahedral cage and shows negligible adsorption capacity of organic dyes, whereas NKU-103 features an open triangular microchannel surrounded by two types of helical chains, and thus exhibits outstanding size-selective adsorption toward small cationic organic dyes.
Co-reporter:Qiang Zhao, Xiu-Ming Liu, Huan-Rong Li, Ying-Hui Zhang and Xian-He Bu
Dalton Transactions 2016 vol. 45(Issue 26) pp:10836-10841
Publication Date(Web):06 Jun 2016
DOI:10.1039/C6DT01161F
A polydentate pyridyl derivative, 2,3,6,7,10,11-hexa(2-pyridyl)-dipyrazino [2,3-f:2′,3′-h]quinoxaline (HPDQ), exhibits a high-performance fluorescence response to La3+ with an ∼65 nm redshifted emission wavelength and 38 fold enhanced intensity, in contrast to its weakened emission for other lanthanide ions. The final La3+ coordination complex in solution has a stoichiometric ratio of 1:3 of ligand-to-metal, as testified by the Job's plot and single crystal structure analyses. The red shift of the luminescence emission as well as UV-vis absorption was rationalized in terms of the change of the electron structure as indicated by nuclear magnetic titration, electrochemical experiment and density functional theoretical calculation, while the significant enhancement of emission was attributed to the enhanced π conjugated extent of HPDQ caused by La3+ coordination.
Co-reporter:Jun-Ying Weng;Yue-Ling Xu;Wei-Chao Song
Journal of Polymer Science Part A: Polymer Chemistry 2016 Volume 54( Issue 12) pp:1724-1730
Publication Date(Web):
DOI:10.1002/pola.28028
ABSTRACT
Aiming at tuning the adsorption and fluorescence properties of targeted porous organic polymer, four new aminal-linked porous organic polymers (NAPOPs) were synthesized through the reaction of 1,4-Bis(4,6-diamino-s-triazin-2-yl) benzene (BATB) with four kinds of aldehydes substituted with different N-heterocyclic groups. Among the polymers, NAPOP-3 decorated with 5-phenyl-tetrazole group shows the largest CO2 adsorption capacity (2.52 mmol g−1 at 273 K and 100 kPa) because of its relative large surface area, while NAPOP-1 decorated with piperazine groups shows relative large CO2/N2 adsorption selectivity (77 at 273 K and 100 kPa), attributable to its large CO2 adsorption heats and cabined pore (<4 Å). Meanwhile, NAPOP-1 and −3 exhibit high adsorption rate toward iodine with a high capacity (>240 wt %). In addition, different luminescence emissions were also observed for NAPOPs, indicating different intramolecular charger transfer occurred inside polymer networks. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1724–1730
Co-reporter:Ting-Ting Zhou, Zhi-Hong Xuan, Da-Shuai Zhang, Ze Chang, Ying-Hui Zhang and Xian-He Bu
CrystEngComm 2015 vol. 17(Issue 31) pp:5884-5888
Publication Date(Web):01 Jul 2015
DOI:10.1039/C5CE01047K
A novel “cage-in-cage” metal–organic framework based on nested cages originated from two-fold interpenetrated networks was reported, which indicates the potential of interpenetration in structure modulation of cage-based MOFs.
Co-reporter:Zhen-Xin Zhao, Yun-Wu Li, Sui-Jun Liu, Li-Fu Wang, Ze Chang, Jian Xu and Ying-Hui Zhang
CrystEngComm 2015 vol. 17(Issue 23) pp:4301-4308
Publication Date(Web):29 Apr 2015
DOI:10.1039/C5CE00649J
Five new CoII/ZnII coordination polymers (CPs), namely [Co(tdzdc)(4,4′-bipy)(H2O)]n (1), {[Co(tdzdc)(bpp)(H2O)]·3H2O}n (2), {[Zn2(tdzdc)2(4,4′-bipy)(H2O)2]·3H2O}n (3), [Zn2(tdzdc)2(obpy)(H2O)2]n (4) and [Zn(tdzdc)(tmb)]n (5), have been synthesized based on the primary ligand 1,2,5-thiadiazole-3,4-dicarboxylic acid (H2tdzdc) together with four selected N/O-donor auxiliary ligands, i.e., 4,4′-bipy: 4,4′-bipyridine, bpp: 1,3-bi(pyridin-4-yl)propane, obpy: [4,4′-bipyridine]-N,N′-dioxide, and tmb: 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene. Single-crystal structural analyses unveil different topologies and interpenetration degrees of 1–5, associated with four different kinds of coordination modes of H2tdzdc that depend on the auxiliary ligands used. CPs 1–4 are all constructed by extending the one-dimensional metal–ligand chain through the respective auxiliary ligands. Among them, the linear rigid auxiliary ligands (i.e., bipy and obpy) generate two-dimensional planes of 1, 3 and 4, which exhibit different interpenetration degrees of 0, 2 and 3, respectively, while the flexible bpp auxiliary ligand forms a three-dimensional net of 2. In contrast, CP 5 has a basic structural unit comprising dinuclear metal clusters that facilitate the formation of a 3-fold interpenetrated two-dimensional net extended through the tmb auxiliary ligand. Furthermore, magnetic investigations of the two CoII-based CPs reveal that despite being mediated by syn–anti bridging of the carboxylate, both 1 and 2 display antiferromagnetic and canted antiferromagnetic behaviors, respectively.
Co-reporter:Yan-Qing Liu, Guo-Jian Ren, Ying-Hui Zhang, Jian Xu and Xian-He Bu
Dalton Transactions 2015 vol. 44(Issue 47) pp:20361-20366
Publication Date(Web):29 Sep 2015
DOI:10.1039/C5DT02987B
Upon solvothermal reactions between Cd(II) salt and 5-pyridyl-tetrazolate (4-Ptz) under different reaction conditions, three new Cd(II) metal–organic frameworks (MOFs), namely [Cd3(4-Ptz)5(H2O)2(μ3-OH)·3DMA·5H2O·CH3OH]n (1), [Cd5(4-Ptz)8(CH3OH)2(μ3-OH)2·2DMA·4H2O·3CH3OH]n (2) and [{Cd9(4-Ptz)14(AC)2(μ3-OH)2(H2O)4}·8DMA·H2O·3CH3OH]n (3), were synthesized based on different highly connected secondary building units (SBUs). In the presence of triethylamine, 1 was constructed based on an 8-connected triangular trinuclear Cd3 SBU and exhibits a three-dimensional framework, while 2 was generated upon the addition of HCl, assembled through a close packing of the octahedron cages consisting of unprecedented 12-connected 4-Ptz bridged Cd5 SBUs and thus showing high thermal and chemical stability. For generating 3, two different kinds of Cd3 SBUs, including an 8-connected triangular SBU and a 10-connected linear SBU, were constructed and further integrated into a distorted octahedron-based net under the addition of both triethylamine and NaCl. In addition to the structural analysis, we also focused on the investigation of gas adsorption and solid-state fluorescence properties of 2.
Co-reporter:Jie Han, Xia Fan, Zhan-Zhong Zhuang, Wei-Chao Song, Ze Chang, Ying-Hui Zhang and Xian-He Bu
RSC Advances 2015 vol. 5(Issue 20) pp:15350-15353
Publication Date(Web):27 Jan 2015
DOI:10.1039/C4RA13696A
A triphenylene-based conjugated microporous polymer (TP-CMP) has been synthesized and shows high surface area (SBET = 1104 m2 g−1) and remarkable uptakes of H2 (7.08 mmol g−1 at 77 K and 900 mmHg) and CO2 (3.37 mmol g−1 at 273 K and 900 mmHg). In addition, it could be utilized to detect nitrobenzene selectively via fluorescence quenching.
Co-reporter:Jun-Jie Wang, Ren-Chun Zhang, Dao-Jun Zhang, Yun-Feng Shi, Ying-Hui Zhang, Xiao-Li Lu, Er-Ni Wang, Feng Jin
Inorganica Chimica Acta 2015 Volume 427() pp:240-247
Publication Date(Web):1 March 2015
DOI:10.1016/j.ica.2015.01.010
•Four MOFs with Htpim have been synthesized and characterized.•Complexes of Htpim are tunable through controlling reaction conditions.•Fluorescence quenching phenomena of 1–2 are observed due to effects of CuI or CuII.•Intense luminescent emissions of 3–4 are attributed to the LLCT of Htpim.Four metal–organic frameworks with 4,4′,4″-(1H-imidazole-2,4,5-triyl)tripyridine (Htpim), namely {[Cu4(tpim)4](DMAC)(H2O)3}∞ (1), {[Cu(H2tpim)2(H2O)2](NO3)4(H2O)2}∞ (2), {[Zn(Htpim)2(H2O)2](NO3)2(H2O)5}∞ (3) and {[Zn(Htpim)(NO3)(H2O)](NO3)}∞ (4) (DMAC = N,N-dimethylacetamide), have been prepared under solvothermal conditions. Single crystal X-ray diffraction analysis indicates that the ligand Htpim adopts ionized form in 1, protonated form in 2, and primary form both in 3 and 4, respectively, with three types of binding modes including μ2-Npy,Npy mode in 2 and 3, μ3-Npy,Npy,Nim mode in 1 and μ3-Npy,Npy,Npy mode in 4. Different network structures, a 2D 3,4-connected {4.62}2{42.62.82} network of 1, a 1D linear chain of 2 and 3, and a 2D 63 framework of 4, were observed and attributed to different synthetic conditions or metal ions. Nitric acid was used not only to adjust the pH value of reaction system, but also to act as a coordination component in 2–4. Furthermore, luminescent properties have also been studied for these four complexes.Four MOFs, showing 1D linear chain, 2D {4.62}2{42.62.82} network and 2D 63 network, have been successfully constructed by Htpim. The discrepancy of synthetic routes and metal-coordination preferences facilitates the production of the final crystalline materials with distinct structures. Moreover, the fluorescence quenching phenomenon of 1 and 2 are observed due to effects of CuI or CuII ions. Intense luminescent emissions of 3 and 4 are attributed to the LLCT of Htpim.
Co-reporter:Rong-Mei Wen, Song-De Han, Hao Wang, Ying-Hui Zhang
Chinese Chemical Letters 2014 Volume 25(Issue 6) pp:854-858
Publication Date(Web):June 2014
DOI:10.1016/j.cclet.2014.05.026
A coordination polymer formulated as {[Mn2L(N3)4]·2H2O}n(1) [L = 1,4-bis(pyridinil-3-carboxylato)-l,4-dimethylbenzene] was synthesized and structurally and magnetically characterized. The uniform Mn(II) chains with mixed (μ-EO-N3)2(μ-COO) triple bridges (EO = end-on) are linked by L ligands to generate a 2-fold interpenetrating 3D framework. Meanwhile, magnetism analysis reveals antiferromagnetic coupling for 1.A coordination polymer formulated as {[Mn2L(N3)4]·2H2O}n (1) [L = 1,4-bis(pyridinil-3-carboxylato)-l,4-dimethylbenzene] was synthesized and characterized. The uniform Mn(II) chains with mixed (μ-EO-N3)2(μ-COO) triple bridges (EO = end-on) are linked by L ligands to generate a 2-fold interpenetrating 3D framework and magnetism analysis reveals dominant antiferromagnetic coupling for 1.
Co-reporter:Jun-Jie Wang, You-Juan Zhang, Jing Chen, Ying-Hui Zhang
Inorganica Chimica Acta 2014 Volume 411() pp:30-34
Publication Date(Web):24 February 2014
DOI:10.1016/j.ica.2013.11.016
•Four isostructural metal–organic compounds were constructed.•Biphenyl groups of ligands play an important role in the formation of frameworks.•The magnetic and luminescent properties of these compounds were studied.Four new coordination polymers, namely [Mn(L)2(H2O)2]∞ (1), [Co(L)2(H2O)2]∞ (2), [Zn(L)2(H2O)2]∞ (3) and [Cd(L)2(H2O)2]∞ (4) (L = biphenyl-4-carboxylate), were synthesized and structurally characterized by elemental analyses, IR spectra, X-ray powder diffraction and single crystal X-ray diffraction analysis. Structural analyses show that 1–4 all assume isostructural two-dimensional (2D) 44 networks. The results indicate that non-coordinating biphenyl groups of ligands play an important role in governing the formation of the final frameworks. There exist antiferromagnetic coupling interactions between the MII ions in 1 as well as in 2. Moreover, intense luminescent emissions of 3 and 4 were attributed to the ligand-to-ligand charge transfer (LLCT).Graphical abstractFour new metal–organic compounds, showing isostructural 2D 44 networks, have been successfully constructed by using biphenyl-4-carboxylate ligands. The results indicate that biphenyl groups of ligands play an important role in governing the formation of the final 2D frameworks. And the magnetic and luminescent properties of corresponding compounds were studied.
Co-reporter:Zhen-Xin Zhao;Bu-Wei Ma;Bo-Yu Zhou;Li-Fu Wang
Journal of Chemical Crystallography 2014 Volume 44( Issue 9) pp:443-449
Publication Date(Web):2014 September
DOI:10.1007/s10870-014-0535-1
1,2,5-thiadiazole-3,4-dicarboxylic acid (H2tdzdc) ligand has been used to construct three coordination compounds [Mg(tdzdc)(H2O)4](1), [Ca(tdzdc)(H2O)2]n(2) and [Sr(tdzdc)(H2O)3]n(3) by the solvothermal reaction. Single-crystal structure analyses reveal a mononuclear coordination structure for compound 1 and two dimensional coordination structure both for compound 2 and 3. Furthermore, all of these three compounds comprise any amount of hydrogen bond interactions, which extends their crystal structure into three dimensional (3D) frameworks. Different crystal structure of compounds 1–3 reveals diversified coordination modes of H2tdzdc ligand toward alkaline earth metal ions, depending mainly on the radius and the electron shell number of metal ions used.
Co-reporter:Jun-Jie Wang, You-Juan Zhang, Ze Chang, Ying-Hui Zhang
Chinese Chemical Letters 2013 Volume 24(Issue 4) pp:270-272
Publication Date(Web):April 2013
DOI:10.1016/j.cclet.2013.03.010
A two-dimensional (2D) 3,3,3,4,5,5,6-connected ZnII coordination compound [Zn5(L)2(OH)6]∞ (L = 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylate) has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single crystal X-ray diffraction analysis. Moreover, the luminescent properties of the ligand and corresponding compound have been briefly investigated.A two-dimensional (2D) ZnII coordination compound [Zn5(L)2(OH)6]∞ (L = 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylate) has been synthesized and characterized, which assumes a 3,3,3,4,5,5,6-connected {4.62}4{42.64}2{42.68}2{43.67}2{43}2{44.67.84} topology network.
Co-reporter:Li-Hong Zhao, Jun-Ying Weng, Wei Zhao, Wen-Juan Ruan, Fei Xin, Ying-Hui Zhang
Chemical Physics 2013 Volume 423() pp:43-48
Publication Date(Web):23 September 2013
DOI:10.1016/j.chemphys.2013.06.015
Highlights
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DFT calculations on porphine/C60 bisadducts were carried out.
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Pyrrolidine ring appended on C60 has influence on its interaction with porphine.
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Interaction was found between pyrrolidine ring appended on C60 and porphyrin.
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Charger transfer between pyrrolidine ring and porphine was observed.
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The red shift of absorption was predicted for fullerene/porphine complexes.
Co-reporter:Ying-Hui Zhang, Li-Hong Zhao, Wen-Juan Ruan, Yao Xu
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2011 Volume 79(Issue 5) pp:1449-1460
Publication Date(Web):September 2011
DOI:10.1016/j.saa.2011.04.085
DFT and TDDFT calculations with density functionals (PBE1PBE, B3LYP, and PBEPBE) have been employed in a study of HCl-acidified diacids of a series of meso-phenylporphyrins. This study aims to clarify the influence of conformational distortion, meso-phenyl substituents, and counterion Cl− on absorption spectra of porphyrin derivatives. Calculations indicate that all three factors increase the MO's level and decrease the Gouterman HOMO–LUMO gap; this, further, brings about the redshift of absorption band. In comparison with experimental methods, the PBE1PBE method produces a more credible description of UV–vis spectra than other two methods. TDDFT calculation with the PBE1PBE method indicates that the electronic effect of the meso-phenyl group is dominant for the spectral redshift of porphyrin diacid series as observed in zinc porphyrins. The redshift of the B band of porphyrin diacids is primarily caused by an electron-donating effect of the meso-phenyl group, whereas the Q band is more sensitive to the π electron delocalization effect. The counterion is indispensable in a theoretical study of electronic and spectral structure of porphyrin diacids.Graphical abstractHighlights► Electronic structure of meso-phenylporphyrin diacids was studied. ► Absorption spectra of meso-phenylporphyrin diacids were simulated. ► The absorption redshift of porphyrin diacids was analyzed. ► Electronic effect of substituent is the key cause to the absorption redshift.
Co-reporter:Ying-Hui Zhang, Wei Zhao, Jin Wang, Ping Jiang
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2010 Volume 75(Issue 2) pp:499-506
Publication Date(Web):February 2010
DOI:10.1016/j.saa.2009.09.016
The vibrational spectra of nickel and zinc 5,10-diphenylporphyrin (NiDaPP and ZnDaPP) have been studied by density functional theory (B3LYP/6-31G(d)) and experimental measurement. The assignment of observed Raman and IR bands are proposed based on theoretical calculation. Theoretical study indicates that 5,10-diphenyl substitution together with out-of-plane distortion diversify the structure of four pyrrole rings and the environment around Cm atoms, which lowers the symmetry of porphyrin skeleton and brings about some variation to vibrational spectra. The first is the activation of all normal modes both in Raman and IR spectra. The second is the lifting of original degenerate Eu representation and its splitting into two A modes in NiDaPP (C1 group point) and A′/A″ presentation in ZnDaPP (Cs group point), respectively. Furthermore, one or both of the two split components, especially for some vibration involving the motion of Cm atom, undergoes further mixing with original non-degenerate mode (A1g, A2g, B1g, or B2g) of same vibration. This produces new modes involving only partial motion of original mode. Besides general increasing frequency of NiDaPP with respect to ZnDaPP, different vibrational structure is also indicated by calculation for some structure-sensitive bands, especially ν8 mode that couples with γ6 mode and split into two modes for NiDaPP but not for ZnDaPP.
Co-reporter:Ying-Hui Zhang, Wei Zhao, Ping Jiang, Long-Jin Zhang, Tao Zhang, Jin Wang
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2010 Volume 75(Issue 2) pp:880-890
Publication Date(Web):February 2010
DOI:10.1016/j.saa.2009.12.027
The influences of meso-phenyl substitution on the geometric structure and vibrational spectra have been studied by DFT calculation (B3LYP/6-31G(d)) and experiment on a series of zinc porphyrins (ZnTPP: zinc 5,10,15,20-tetraphenylporphyrin; ZnTrPP: zinc 5,10,15-triphenylporphryin; ZnDPP: zinc 5,15-dipenylporphyirn; ZnMPP: zinc 5-monophenylporphyrin; ZnP: zinc porphine). Calculation indicates that meso-phenyl substitution gives rise to slight out-of-plane distortion but significant in-plane distortion, especially for the configuration around Cm atom, to zinc porphyrin. The assignment of experimental vibrational spectra was proposed mainly on the basis of calculation. Different shifting tendency upon meso-phenyl substitution is observed for different structure-sensitive bands, such as the shifting of ν2, ν3, ν6, and ν8 modes toward higher frequencies and ν4 and ν28 modes toward lower frequencies, upon meso-phenyl substitution. This is attributed primarily to in-plane nuclear reorganization effect (IPNR), though the contribution from out-of-plane distortion cannot be excluded completely. Analysis on vibrational structure reveals that asymmetric meso-phenyl substitution, especially the 5,15-diphenyl substitution of ZnDPP, brings about asymmetric vibrational displacement, or even splitting of vibrational structure to normal modes involving mainly the motion of meso-Cm. This is ascribed to the reduction of symmetry of porphyrin skeleton caused by asymmetric meso-phenyl substitution.
Co-reporter:Ying-Hui Zhang, Wen-Juan Ruan, Zhi-Yun Li, Yang Wu, Jian-Yu Zheng
Chemical Physics 2005 Volume 315(1–2) pp:201-213
Publication Date(Web):8 August 2005
DOI:10.1016/j.chemphys.2005.04.004
Abstract
The influence of meso-phenyl substitution on the geometric, electronic structure and vibrational spectra of free base porphyrin were studied by DFT calculation and experimental observation on a series of meso-phenylporphyrins: 5-monophenylporphine (H2MPP), 5,15-diphenyporphine (H2DOPP), 5,10-diphenyl porphine (H2DAPP), 5,10,15-triphenylporphine (H2TrPP), and 5,10,15,20-tetraphenylporphine (H2TPP). Theoretical calculation indicates that meso-phenyl substitution brings about significant in-plane distortion to porphyrin ring, whereas the resulted out-of-plane distortion is negligible. Thus, the observed redshift of electronic absorption peaks (both B and Q bands) upon increasing meso-phenyl substitution, which is also indicated by theoretical calculation, was attributed to in-plane nuclear reorganization (IPNR) induced by phenyl-substitution rather than nonplanarity mechanism, though the contribution of the latter could not be excluded completely. The vibrational spectra analysis (both Raman and IR spectra) indicates that meso-phenyl substitution results in different evolution for different vibrational modes of porphyrin ring. For example, both experiment and calculation shows the great downshift of ν10 and ν28 modes and the upshift of some other structure-sensitive bands (for instance ν2, ν6, ν15, and ν8 modes) in different extent. This evolution differs from the downshift of structure-sensitive bands (for instance ν2 and ν3 mode) caused by nonplanarity mechanism, and was also attributed to IPNR mechanism rather than nonplanarity mechanism. Further comparison indicates that calculation predicted shift of vibrational frequencies are consistent well with experimental observation, which indicates that DFT calculation at B3LYP/6-31G(d) level give convincible prediction on substitution-resulted frequency evolution of porphyrin.
Co-reporter:Ying-Hui Zhang, Zhi-Yun Li, Yang Wu, Yi-Zhou Zhu, Jian-Yu Zheng
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2005 Volume 62(1–3) pp:83-91
Publication Date(Web):November 2005
DOI:10.1016/j.saa.2004.12.009
The ground state geometric, electronic structure and Raman spectra of 5,15-diphenylporphine (H2DPP) have been studied using B3LYP/6-31G(d) method and compared with that of well-studied free base porphine (H2P) and meso-tetraphenylporphine (H2TPP). Calculation shows that 5,15-substitution causes remarkable in-plane distortion, whereas the resulting out-of-plane distortion is negligible. The calculated electronic structure of H2DPP is consistent with the absorption spectra compared with H2P and H2TPP. The calculated vibrational frequencies of H2DPP scaled with a single factor of 0.971 agree well with experimental data (the rms error is 8.0 cm−1). The assignment of experimental Raman bands of H2DPP was discussed on the basis of theoretical calculation and the comparison with that of H2P and H2TPP. The splitting of some vibrational modes involving the motion of Cm atom, such as ν1, ν8, and ν10, was observed and was attributed to the diversification of the environment around Cm atoms. As the shift of absorption peaks, the shift of some structure-sensitive Raman bands of H2DPP form that of H2TPP and H2P was attributed to the in-plane nuclear reorganization (IPNR) induced by phenyl-substitution, though the contribution of nonplanarity mechanism could not be excluded completely.
Co-reporter:Yue-Ling Xu, Qiang Gao, Meng Zhao, Huan-Jun Zhang, Ying-Hui Zhang, Ze Chang
Chinese Chemical Letters (January 2017) Volume 28(Issue 1) pp:55-59
Publication Date(Web):January 2017
DOI:10.1016/j.cclet.2016.06.006
Co-reporter:Qiang Zhao, Xiu-Ming Liu, Huan-Rong Li, Ying-Hui Zhang and Xian-He Bu
Dalton Transactions 2016 - vol. 45(Issue 26) pp:NaN10841-10841
Publication Date(Web):2016/06/06
DOI:10.1039/C6DT01161F
A polydentate pyridyl derivative, 2,3,6,7,10,11-hexa(2-pyridyl)-dipyrazino [2,3-f:2′,3′-h]quinoxaline (HPDQ), exhibits a high-performance fluorescence response to La3+ with an ∼65 nm redshifted emission wavelength and 38 fold enhanced intensity, in contrast to its weakened emission for other lanthanide ions. The final La3+ coordination complex in solution has a stoichiometric ratio of 1:3 of ligand-to-metal, as testified by the Job's plot and single crystal structure analyses. The red shift of the luminescence emission as well as UV-vis absorption was rationalized in terms of the change of the electron structure as indicated by nuclear magnetic titration, electrochemical experiment and density functional theoretical calculation, while the significant enhancement of emission was attributed to the enhanced π conjugated extent of HPDQ caused by La3+ coordination.
Co-reporter:Yan-Qing Liu, Guo-Jian Ren, Ying-Hui Zhang, Jian Xu and Xian-He Bu
Dalton Transactions 2015 - vol. 44(Issue 47) pp:NaN20366-20366
Publication Date(Web):2015/09/29
DOI:10.1039/C5DT02987B
Upon solvothermal reactions between Cd(II) salt and 5-pyridyl-tetrazolate (4-Ptz) under different reaction conditions, three new Cd(II) metal–organic frameworks (MOFs), namely [Cd3(4-Ptz)5(H2O)2(μ3-OH)·3DMA·5H2O·CH3OH]n (1), [Cd5(4-Ptz)8(CH3OH)2(μ3-OH)2·2DMA·4H2O·3CH3OH]n (2) and [{Cd9(4-Ptz)14(AC)2(μ3-OH)2(H2O)4}·8DMA·H2O·3CH3OH]n (3), were synthesized based on different highly connected secondary building units (SBUs). In the presence of triethylamine, 1 was constructed based on an 8-connected triangular trinuclear Cd3 SBU and exhibits a three-dimensional framework, while 2 was generated upon the addition of HCl, assembled through a close packing of the octahedron cages consisting of unprecedented 12-connected 4-Ptz bridged Cd5 SBUs and thus showing high thermal and chemical stability. For generating 3, two different kinds of Cd3 SBUs, including an 8-connected triangular SBU and a 10-connected linear SBU, were constructed and further integrated into a distorted octahedron-based net under the addition of both triethylamine and NaCl. In addition to the structural analysis, we also focused on the investigation of gas adsorption and solid-state fluorescence properties of 2.
