TY - JOUR

T1 - One-dimensional Zn(II) oligo(phenyleneethynylene)dicarboxylate coordination polymers

T2 - Synthesis, crystal structures, thermal and photoluminescent properties

AU - Schaate, Andreas

AU - Schulte, Miriam

AU - Wiebcke, Michael

AU - Godt, Adelheid

AU - Behrens, Peter

PY - 2009/4/10

Y1 - 2009/4/10

N2 - The rigid, π-conjugated dicarboxylic acid 1,4-bis-[2-(4-carboxyphenyl)ethynyl]-2,5-dihexylbenzene {HO2C[PEP(hexyl)2EP]CO2H} has been used to synthesise the new crystalline coordination polymers {Zn(O2C[PEP(hexyl)2EP]CO2)(DMF)2} (1) and {Zn(O2C[PEP(hexyl)2EP]CO2)(DEF)2} (2) in N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF), respectively, under mild conditions. Single-crystal X-ray crystallography revealed that 1 and 2 are isostructural and consist of uncharged zigzag coordination chains in which [Zn(formamide)2]2+ fragments are bridged by (O2C[PEP(hexyl)2EP]CO2)2- ligands. The zigzag chains possess different intra-chain Zn⋯Zn⋯Zn angles due to the different volumes of the coordinating formamide molecules and subtle differences in the hydrophobic inter-chain interactions. Upon heating 1 and 2 to 200 °C, removal of the coordinating formamide molecules occurs, yielding the formamide-free compounds 1-DMF and 2-DEF of composition {Zn(O2C[PEP(hexyl)2EP]CO2)}. According to powder X-ray diffraction and FT-IR spectroscopy studies, these materials are not crystalline but still possess partial ordering of intact, yet modified coordination chains in a structural arrangement which appears to be related to the respective parent compounds. Compounds 1, 2, 1-DMF and 2-DEF exhibit blue photoluminescence. The emission maxima of 1-DMF and 2-DEF are red-shifted by ca. 25 nm with respect to λmax of 1 and 2, respectively.

AB - The rigid, π-conjugated dicarboxylic acid 1,4-bis-[2-(4-carboxyphenyl)ethynyl]-2,5-dihexylbenzene {HO2C[PEP(hexyl)2EP]CO2H} has been used to synthesise the new crystalline coordination polymers {Zn(O2C[PEP(hexyl)2EP]CO2)(DMF)2} (1) and {Zn(O2C[PEP(hexyl)2EP]CO2)(DEF)2} (2) in N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF), respectively, under mild conditions. Single-crystal X-ray crystallography revealed that 1 and 2 are isostructural and consist of uncharged zigzag coordination chains in which [Zn(formamide)2]2+ fragments are bridged by (O2C[PEP(hexyl)2EP]CO2)2- ligands. The zigzag chains possess different intra-chain Zn⋯Zn⋯Zn angles due to the different volumes of the coordinating formamide molecules and subtle differences in the hydrophobic inter-chain interactions. Upon heating 1 and 2 to 200 °C, removal of the coordinating formamide molecules occurs, yielding the formamide-free compounds 1-DMF and 2-DEF of composition {Zn(O2C[PEP(hexyl)2EP]CO2)}. According to powder X-ray diffraction and FT-IR spectroscopy studies, these materials are not crystalline but still possess partial ordering of intact, yet modified coordination chains in a structural arrangement which appears to be related to the respective parent compounds. Compounds 1, 2, 1-DMF and 2-DEF exhibit blue photoluminescence. The emission maxima of 1-DMF and 2-DEF are red-shifted by ca. 25 nm with respect to λmax of 1 and 2, respectively.

KW - Coordination polymer

KW - Crystal structure

KW - Oligo(phenyleneethynylene)dicarboxylic acid

KW - Photoluminescence

KW - Zinc

UR - http://www.scopus.com/inward/record.url?scp=67349083610&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2009.04.004

DO - 10.1016/j.ica.2009.04.004

M3 - Article

AN - SCOPUS:67349083610

VL - 362

SP - 3600

EP - 3606

JO - Inorganica chimica acta

JF - Inorganica chimica acta

SN - 0020-1693

IS - 10

ER -