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Tetragonal Diiodotetrapyridinedicopper(I): Structure, Luminescence, and Computational Modeling

  • Andrew W. Kelly
  • Joseph V. Handy
  • Aaron D. Nicholas
  • Francis H. Barnes
  • Howard H. Patterson
  • Lukasz Wojtas
  • Robert D. Pike
Article

Abstract

We report on a new crystal modification of (CuIPy2) n (Py = pyridine), a compound first reported by White et al. In contrast to White’s orthorhombic structure, which is comprised of rhomboid iodide-bridged dimers, Cu2I2Py4, our new tetragonal crystal structure in space group P41212 is disordered and can be interpreted as either iodide-bridged dimers or helical chains. To determine the structure type, variable temperature X-ray diffraction and luminescence measurements were carried out. The photoluminescence spectrum shows a distinct cluster-centered transition at high excitation energies which is consistent with the dimer structure. DFT and TD-DFT calculations were performed to explain the difference between the emission spectrum at high energies compared to low energies. Furthermore, correlation of the luminescence spectrum with the X-ray results as temperature is varied demonstrates that the cluster-centered luminescence band in Cu2I2Py4 arises from close Cu⋯Cu distances which vary with temperature. A low temperature X-ray crystallographic redetermination of the cubane tetrameric Cu4I4Py4 is also presented. Both Cu2I2Py4 and Cu4I4Py4 structures show distortion of the Cu n I n core cluster at low temperature resulting in reduced Cu⋯Cu distances, but with I⋯I distances roughly unchanged.

Keywords

Copper(I) iodide Pyridine Dimer Polymorph Luminescence X-ray crystal structure Density functional theory 

Notes

Acknowledgements

We are indebted to NSF (CHE-0443345) and the College of William and Mary for the purchase of the X-ray equipment.

Supplementary material

10904_2017_584_MOESM1_ESM.docx (3.8 mb)
Crystallographic information on CCDC 1529200-1529204 can be obtained free of charge by e-mailing data_request@ccdc.cam.ac.uk or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ UK; Fax +44(0)1223-336033; www.ccdc.cam.ac.uk/data_request/cif (DOCX 3897 KB)

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Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • Andrew W. Kelly
    • 1
  • Joseph V. Handy
    • 1
  • Aaron D. Nicholas
    • 2
  • Francis H. Barnes
    • 2
  • Howard H. Patterson
    • 2
  • Lukasz Wojtas
    • 3
  • Robert D. Pike
    • 1
  1. 1.Department of ChemistryCollege of William and MaryWilliamsburgUSA
  2. 2.Department of ChemistryUniversity of MaineOronoUSA
  3. 3.Department of ChemistryUniversity of South FloridaTampaUSA

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