How do substituent groups in the 5-position of 1,3-benzenedicarboxylate affect the construction of supramolecular frameworks?Electronic supplementary information (ESI) available: Additional data. CCDC reference numbers 749194–749197. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c005322h

Four 1,3-benzenedicarboxylic acid derivatives, with substituted R (OH, COOH, NO2, Me) groups at the 5-position, were employed to explore their effect on the construction of supramolecular assemblies. Four coordination polymers, [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]n(1), [Zn(1,3,5-HBTC)(1,4-bpeb)]n(2), {[Zn(5-NO2-1,3-BDC)(1,4-bpeb)]·2(H2O)0.5}n(3), and [Zn(5-Me-1,3-BDC)(1,4-bpeb)]n(4) (1,4-bpeb = 1,4-bis[2-(4-pyridyl)ethenyl]benzene, 5-HO-1,3-BDC = 5-hydroxy-1,3-benzenedicarboxylate, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylate, 5-NO2-1,3-BDC = 5-nitro-1,3-benzenedicarboxylate, 5-Me-1,3-BDC = 5-methyl-1,3-benzenedicarboxylate) were prepared by the hydrothermal reactions of Zn(NO3)2·6H2O with 1,4-bpeb and 5-HO-1,3-H2BDC, 1,3,5-H3BTC, 5-NO2-1,3-H2BDC or 5-Me-1,3-H2BDC. All these compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of 1has a 3D H-bonded structure derived from linking 1D comb-like [Zn(OH2)(5-HO-1,3-BDC)(1,4-bpeb)]nchains viaintermolecular H-bonding interactions between the coordinated H2O molecule and 1,4-bpeb or one COO−group and between the OH group and the other COO−group. 2has a 3D H-bonded net based on holding 2D [{Zn2(1,3,5-HBTC)2}4]nlayers through intermolecular H-bonding interactions between 1,4-bpeb and the uncoordinated COOH group. 3could be considered as a 6-fold interpenetrating 3D H-bonded supramolecular framework constructed by linking 2D [Zn4(5-NO2-1,3-BDC)4(1,4-bpeb)4]nnetworks through intermolecular H-bonding interactions between the water solvent molecules and the NO2group. 4has a 3-fold interpenetrating 3D framework in which each 2D (4,4) [Zn4(5-Me-1,3-BDC)4(1,4-bpeb)4]nnetwork is interpenetrated by two other equivalent nets. The Schläfli symbols for the four supramolecular frameworks are 41263, (4·62)2(426687), (63)(658) and 4462, respectively. The thermal stability and photoluminescent properties of 1–4were also investigated. [ABSTRACT FROM AUTHOR]