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Influence of Metal Cations and Coordination Modes on Luminescent Group 1 and 2 Metal Sulfonate Complexes Constructed from 4,4′‐Dihydroxybiphenyl‐3,3′‐disulfonic Acid
Author(s) -
Yu YiZhe,
Li YaNan,
Deng ZhaoPeng,
Zhu ZhiBiao,
Huo LiHua,
Gao Shan
Publication year - 2015
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.201500170
Subject(s) - chemistry , sulfonate , aqueous solution , crystallography , supramolecular chemistry , metal , hydrogen bond , crystal structure , luminescence , coordination sphere , thermogravimetry , stereochemistry , medicinal chemistry , inorganic chemistry , molecule , sodium , organic chemistry , physics , optoelectronics
The reactions of 4,4′‐dihydroxybiphenyl‐3,3′‐disulfonic acid (H 4 L) with group 1 and 2 metal salts in aqueous solution lead to six metal sulfonate complexes, [K 2 (H 2 L)] n ( 1 ), {[Cs 2 (H 2 L)(H 2 O)] n · n H 2 O} ( 2 ), 2[Mg(H 2 O) 6 ] 2+ · 2(H 2 L) 2– · 2H 2 O ( 3 ), {[Ca(H 2 L)(H 2 O) 2 ] n · 4 n H 2 O} ( 4 ), {[Sr(H 2 L)(H 2 O) 4 ] n · 3 n H 2 O} ( 5 ), and {[Ba(H 2 L)(H 2 O)] n · n H 2 O} ( 6 ), which have been characterized by elemental analysis, IR spectroscopy, thermogravimetry (TG), photoluminescence (PL) spectroscopy, powder XRD, and single‐crystal XRD. Complexes 1 , 2 , and 6 exhibit 3D pillared‐layered networks formed by M–O–S layers bridged by the biphenyl rings of H 2 L 2– dianions. The [Mg(H 2 O) 6 ] 2+ cations and sulfonate groups in 3 are held together by second‐sphere interactions to generate layer motifs. Complex 4 presents a layer structure formed by Ca–O chains bridged by the biphenyl rings of H 2 L 2 – dianions. Complex 5 has a 3D interdigitating architecture (2D + 2D → 3D), in which the 4 4 hydrogen‐bonding layer is constructed from linear chains. Meanwhile, the recrystallization of H 4 L from aqueous solution affords the supramolecular complex 2(H 3 O + ) · (H 2 L) 2– · 3H 2 O ( S1 ), which exhibits a 3D pillared‐layered network. The solid‐state luminescence properties demonstrate that 1 – 6 exhibit violet emission at room temperature and can sensitize Eu III and Tb III ions to exhibit their characteristic emissions.