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Zinc(II) and Cadmium(II) Coordination Polymers Based on 3‐(5 H ‐Tetrazolyl)benzoate Ligand with Different Coordination Modes: Hydrothermal Syntheses, Crystal Structures and Ligand‐Centered Luminescence
Author(s) -
Chen Feng,
Wu MeiFeng,
Liu GuangNing,
Wang MingSheng,
Zheng FaKun,
Yang Chen,
Xu ZhongNing,
Liu ZhiFa,
Guo GuoCong,
Huang JinShun
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000578
Subject(s) - chemistry , ligand (biochemistry) , luminescence , crystallography , zinc , benzoic acid , hydrothermal synthesis , coordination polymer , crystal structure , stereochemistry , hydrothermal circulation , organic chemistry , biochemistry , physics , receptor , optoelectronics , seismology , geology
Hydrothermal reaction of Na(3‐cba) (3‐cba = 3‐cyanobenzoate), NaN 3 and a metal salt with either 2,2′‐bipyridine (2,2′‐bipy) or 1,10‐phenanthroline (phen) afforded four novel Zn II /Cd II polymers, which have been structurally characterized by single‐crystal X‐ray diffraction analysis. In situ [2 + 3] cycloaddition reaction of nitrile and azide in the presence of a Zn II or Cd II salt yielded the ligand 3‐(5 H ‐tetrazolyl)benzoate (3‐tzba 2– ) [3‐H 2 tzba = 3‐(5 H ‐tetrazolyl)benzoic acid]. The obtained polymers are formulated as [Zn 2 (3‐tzba)(N 3 )(OH)(2,2′‐bipy)] ( 1 ), [Zn(3‐tzba)(2,2′‐bipy)(H 2 O)] · 3H 2 O ( 2 ), [Zn 2 (3‐tzba) 2 (phen) 2 ] · H 2 O ( 3 ) and [Cd 4 (3‐tzba) 2 (N 3 ) 4 (2,2′‐bipy) 3 ] · H 2 O ( 4 ). A crystalline mixture of Zn II polymers 1 and 2 with infinite ladder‐like chain and zigzag chain structures, respectively, was obtained from the reaction in the presence of 2,2′‐bipy. The replacement of 2,2′‐bipy with phen as an auxiliary ligand yielded 3 , which shows a pearl‐necklace‐like chain structure. Further, the introduction of Cd II instead of Zn II resulted in the formation of 4 , which has a 2D corrugated layer structure. The 3‐tzba 2– ligands display four different coordination modes in 1 – 4 , and modes μ 2 ‐κN2:κO1,O2 (in 2 ) and μ 3 ‐κN3:κO1:κO2 (in 3 ) are observed in tetrazolate‐5‐carboxylate polymers for the first time. Photoluminescent studies in the solid state at room and low temperature revealed that 1 – 4 exhibit interesting luminescent behaviors, and the relevant density of states (DOS) calculation results showed that their photoluminescence mainly originates from ligand‐centered emission and is dependent on the organic ligand incorporated into the polymer.