Synthesis, structure and luminescence behaviour of complexes of type [Cd(dpa)2X2] (dpa = 2,2′-dipyridylamine; X = N 3-, NCS-, NCO-)

Habibar Chowdhury, Rajarshi Ghosh, Sk Hafijur Rahaman, Georgina M. Rosair, Barindra K. Ghosh

Research output: Contribution to journalArticle

Abstract

The synthetic details and characterization data of three mononuclear complexes of the type [Cd(dpa)2X2] (dpa = 2,2'-dipyridylamine; X = N3-, 1; X = NCS -, 2 and X = NCO-, 3) are described. In one case, [Cd(dpa)2(NCS)2] (2), X-ray structure determination has been made for the exact definition of the coordination sphere. Structural analysis reveals that the cadmium(II) centre is in a distorted octahedral environment with a CdN5S chromophore with two dpa units roughly perpendicular to one another and the two thiocyanates in mutual cis orientation with one in S-bound and the other in N-bound states. The mononuclear unit packs through N-H...S and N-H...N hydrogen bonding to have a one-dimensional (ID) chain. Spectroscopic and other physicochemical data show that compounds 1 and 3 have the cognate structure. The compounds display high energy intraligand 1(p-p*) fluorescence and intraligand 3(p- p*) phosphorescence in glassy solutions (DMF at 77 K). A band (near 375 nm) observed for all the complexes in their solid state emission spectra is an excimeric emission. The role of dpa, a tailored diimine with active amine hydrogen and aromatic pyridine ring, is discussed towards functionalisation on crystal engineering and luminescence behaviour.

Original languageEnglish
Pages (from-to)687-692
Number of pages6
JournalIndian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry
Volume44
Issue number4
Publication statusPublished - Apr 2005

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Thiocyanates
Crystal engineering
Phosphorescence
Chromophores
Cadmium
Structural analysis
Amines
Luminescence
Hydrogen
Hydrogen bonds
Fluorescence
X rays
pyridine
2,2'-dipyridylamine

Cite this

@article{e65514c9570e4e0d8152f62633d35087,
title = "Synthesis, structure and luminescence behaviour of complexes of type [Cd(dpa)2X2] (dpa = 2,2′-dipyridylamine; X = N 3-, NCS-, NCO-)",
abstract = "The synthetic details and characterization data of three mononuclear complexes of the type [Cd(dpa)2X2] (dpa = 2,2'-dipyridylamine; X = N3-, 1; X = NCS -, 2 and X = NCO-, 3) are described. In one case, [Cd(dpa)2(NCS)2] (2), X-ray structure determination has been made for the exact definition of the coordination sphere. Structural analysis reveals that the cadmium(II) centre is in a distorted octahedral environment with a CdN5S chromophore with two dpa units roughly perpendicular to one another and the two thiocyanates in mutual cis orientation with one in S-bound and the other in N-bound states. The mononuclear unit packs through N-H...S and N-H...N hydrogen bonding to have a one-dimensional (ID) chain. Spectroscopic and other physicochemical data show that compounds 1 and 3 have the cognate structure. The compounds display high energy intraligand 1(p-p*) fluorescence and intraligand 3(p- p*) phosphorescence in glassy solutions (DMF at 77 K). A band (near 375 nm) observed for all the complexes in their solid state emission spectra is an excimeric emission. The role of dpa, a tailored diimine with active amine hydrogen and aromatic pyridine ring, is discussed towards functionalisation on crystal engineering and luminescence behaviour.",
author = "Habibar Chowdhury and Rajarshi Ghosh and Rahaman, {Sk Hafijur} and Rosair, {Georgina M.} and Ghosh, {Barindra K.}",
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Synthesis, structure and luminescence behaviour of complexes of type [Cd(dpa)2X2] (dpa = 2,2′-dipyridylamine; X = N 3-, NCS-, NCO-). / Chowdhury, Habibar; Ghosh, Rajarshi; Rahaman, Sk Hafijur; Rosair, Georgina M.; Ghosh, Barindra K.

In: Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, Vol. 44, No. 4, 04.2005, p. 687-692.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, structure and luminescence behaviour of complexes of type [Cd(dpa)2X2] (dpa = 2,2′-dipyridylamine; X = N 3-, NCS-, NCO-)

AU - Chowdhury, Habibar

AU - Ghosh, Rajarshi

AU - Rahaman, Sk Hafijur

AU - Rosair, Georgina M.

AU - Ghosh, Barindra K.

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N2 - The synthetic details and characterization data of three mononuclear complexes of the type [Cd(dpa)2X2] (dpa = 2,2'-dipyridylamine; X = N3-, 1; X = NCS -, 2 and X = NCO-, 3) are described. In one case, [Cd(dpa)2(NCS)2] (2), X-ray structure determination has been made for the exact definition of the coordination sphere. Structural analysis reveals that the cadmium(II) centre is in a distorted octahedral environment with a CdN5S chromophore with two dpa units roughly perpendicular to one another and the two thiocyanates in mutual cis orientation with one in S-bound and the other in N-bound states. The mononuclear unit packs through N-H...S and N-H...N hydrogen bonding to have a one-dimensional (ID) chain. Spectroscopic and other physicochemical data show that compounds 1 and 3 have the cognate structure. The compounds display high energy intraligand 1(p-p*) fluorescence and intraligand 3(p- p*) phosphorescence in glassy solutions (DMF at 77 K). A band (near 375 nm) observed for all the complexes in their solid state emission spectra is an excimeric emission. The role of dpa, a tailored diimine with active amine hydrogen and aromatic pyridine ring, is discussed towards functionalisation on crystal engineering and luminescence behaviour.

AB - The synthetic details and characterization data of three mononuclear complexes of the type [Cd(dpa)2X2] (dpa = 2,2'-dipyridylamine; X = N3-, 1; X = NCS -, 2 and X = NCO-, 3) are described. In one case, [Cd(dpa)2(NCS)2] (2), X-ray structure determination has been made for the exact definition of the coordination sphere. Structural analysis reveals that the cadmium(II) centre is in a distorted octahedral environment with a CdN5S chromophore with two dpa units roughly perpendicular to one another and the two thiocyanates in mutual cis orientation with one in S-bound and the other in N-bound states. The mononuclear unit packs through N-H...S and N-H...N hydrogen bonding to have a one-dimensional (ID) chain. Spectroscopic and other physicochemical data show that compounds 1 and 3 have the cognate structure. The compounds display high energy intraligand 1(p-p*) fluorescence and intraligand 3(p- p*) phosphorescence in glassy solutions (DMF at 77 K). A band (near 375 nm) observed for all the complexes in their solid state emission spectra is an excimeric emission. The role of dpa, a tailored diimine with active amine hydrogen and aromatic pyridine ring, is discussed towards functionalisation on crystal engineering and luminescence behaviour.

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SN - 0376-4710

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