Pressure-induced variations of MLCT and ligand-centered luminescence spectra in square-planar platinum(II) complexes

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• 作者：Alexandre Rodrigue-Witchel^a ; David L. Rochester^b ; Shu-Bin Zhao^c ; Kevin B. Lavelle^d ; J.A. Gareth Williams^b ; Suning Wang^c ; William B. Connick^d ; Christian Reber^a ; ^{christian.reber@umontreal.ca" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Luminescence spectroscopy ; Variable-temperature spectroscopy ; Variable-pressure spectroscopy ; Cyclometallated platinum(II) complexes ; NCN-coordinating ligand
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：29 March 2016
• 年：2016
• 卷：108
• 期：Complete
• 页码：151-155
• 全文大小：1444 K

文摘

Solid-state luminescence spectra of five crystalline platinum(II) complexes at variable pressure and temperature are presented and compared. Maxima occur between 14 000 cm⁻¹ and 15 600 cm⁻¹ (approximately 700–640 nm) at ambient temperature and pressure. Spectra can be broad bands, characteristic of MLCT transitions, or vibronically structured, characteristic of intraligand transitions. Both pressure and temperature variations can lead to distinctive changes in the luminescence spectra that differ between these two types of transitions. MLCT band maxima show shifts on the order of −20 cm⁻¹/kbar to lower energy; in contrast, ligand-centered luminescence bands do not show significant shifts between ambient pressure and 40 kbar.