Selenocyanate Complexes of Cobalt(III), Palladium(II), and Platinum(II)

Burmeister, John L.; Al-Janabi, Monther Y.

doi:10.1021/ic50029a008

Cited by 32 publications

(2 citation statements)

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“…Single crystals of [Pt(SCN) 4 ](PPh 4 ) 2 ( 1 ), [Pt(SCN) 4 ]( n -Bu 4 N) 2 ( 2 ), [Pd(SCN) 4 ]( n -Bu 4 N) 2 ( 3 ), [Pt(SeCN) 4 ]( n -Bu 4 N) 2 ( 4 ), and [Pd(SeCN) 4 ]( n -Bu 4 N) 2 ( 5 ) were prepared following literature methods. ,− Starting materials were purchased from Sigma-Aldrich and used without further purification. Complexes 1 − 3 were also prepared by dissolving crystals of K 2 [PtCl 4 ] or K 2 [PdBr 4 ] in water and adding an aqueous solution of KSCN in excess followed by gentle refluxing for 2 h. After rotary evaporation of water, the potassium salts of the thiocyanate compounds were recrystallized three times from hot 1-butanol.…”

Section: Methodsmentioning

confidence: 99%

Pressure-Induced Enhancements of Luminescence Intensities and Lifetimes Correlated with Emitting-State Distortions for Thiocyanate and Selenocyanate Complexes of Platinum(II) and Palladium(II)

2003

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The luminescence properties of thiocyanate and selenocyanate platinum(II) and palladium(II) complexes show strong variations with temperature and pressure. The d-d luminescence band maxima for [Pt(SCN)(4)](PPh(4))(2) (1), [Pt(SCN)(4)](n-Bu(4)N)(2) (2), and [Pt(SeCN)(4)](n-Bu(4)N)(2) (4) complexes are centered at ca. 14500 cm(-1) whereas those of the [Pd(SCN)(4)](n-Bu(4)N)(2) (3) and [Pd(SeCN)(4)](n-Bu(4)N)(2) (5) complexes are approximately 2000 cm(-1) lower in energy. Low-temperature luminescence spectra from single-crystal samples have broad bands with highly resolved vibronic structure indicating large displacements of the emitting-state potential energy minimum along several metal-ligand normal coordinates. The largest displacements involve the totally symmetric (a(1g)) stretching modes with frequencies of 295 cm(-1) (1), 303 cm(-1) (2), 274 cm(-1) (3), 195 cm(-1) (4), and 185 cm(-1) (5). The lower frequencies of these dominant progression-forming modes for the selenocyanate complexes lead to luminescence bands that are narrower by ca. 500 cm(-1) (fwhm) than those observed from the thiocyanate complexes. Under external pressures, the room-temperature luminescence intensities and lifetimes show considerable enhancement at pressures up to 40 kbar. This effect is largest for the palladium(II) complexes with lifetimes increasing from approximately 350 ns at ambient pressure up to 62 micros at 30 kbar, an increase by more than 2 orders of magnitude. The platinum(II) complexes exhibit a significant, but noticeably lesser increase of luminescence lifetimes and intensities with increasing pressure. The temperature- and pressure-dependent luminescence decay behavior is rationalized using the emitting-state molecular geometry determined from the resolved low-temperature luminescence spectra combined with the strong-coupling limit of radiationless decay theory.

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Section: Methodsmentioning

confidence: 99%

Pressure-Induced Enhancements of Luminescence Intensities and Lifetimes Correlated with Emitting-State Distortions for Thiocyanate and Selenocyanate Complexes of Platinum(II) and Palladium(II)

2003

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“…The Co(II) cations having a d 9 configuration are found in most organometallic compounds in square planar, squarepyramidal, or square-bipyramidal geometries [2]. Thiocyanate (SCN) − is an ambidentate ligand that has been significant in the generation of bonding models for the mechanisms that influence linkage isomerism in transition metal complexes, resulting in a variety of structures of varying dimensions [3,4]. Increasing the diversity of the paramagnetic metal centers used can lead to more exciting magnetic and optic properties [5].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Structure, Hirshfeld Surface Analysis, Morphological Study and DFT Calculations of the Triphenyltetrazolium Cobalt Thiocyanate Complex

Ali,

Bechaieb,

Al-Salahi

et al. 2023

Crystals

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Polymorphism is a prevalent occurrence in pharmaceutical solids and demands thorough investigation during product development. This paper delves into the crystal growth and structure of a newly synthesized polymorph (TPT)2[CoII(NCS)4], (1), where TPT is triphenyl tetrazolium. The study combines experimental and theoretical approaches to elucidate the 3D framework of the crystal structure, characterized by hydrogen-bonded interactions between (TPT)+ cations and [Co(NCS)4]2− anions. Hirshfeld surface analysis, along with associated two-dimensional fingerprints, is employed to comprehensively investigate and quantify intermolecular interactions within the structure. The enrichment ratio is calculated for non-covalent contacts, providing insight into their propensity to influence crystal packing interactions. Void analysis is conducted to predict the mechanical behavior of the compound. Utilizing Bravais-Friedel, Donnay-Harker (BFDH), and growth morphology (GM) techniques, the external morphology of (TPT)2[CoII(NCS)4] is predicted. Experimental observations align well with BFDH predictions, with slight deviations from the GM model. Quantum computational calculations of the synthesized compounds is performed in the ground state using the DFT/UB3LYP level of theory. These calculations assess the molecule’s stability and chemical reactivity, including the computation of the HOMO-LUMO energy difference and other chemical descriptors. The study provides a comprehensive exploration of the newly synthesized polymorph, shedding light on its crystal structure, intermolecular interactions, mechanical behavior, and external morphology, supported by both experimental and computational analyses.

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The Formation, Structure, and Reactions of Binuclear Complexes of Cobalt

Sykes

Weil

1970

Progress in Inorganic Chemistry

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Selenocyanate Complexes of Cobalt(III), Palladium(II), and Platinum(II)

Cited by 32 publications

References 0 publications

Pressure-Induced Enhancements of Luminescence Intensities and Lifetimes Correlated with Emitting-State Distortions for Thiocyanate and Selenocyanate Complexes of Platinum(II) and Palladium(II)

Pressure-Induced Enhancements of Luminescence Intensities and Lifetimes Correlated with Emitting-State Distortions for Thiocyanate and Selenocyanate Complexes of Platinum(II) and Palladium(II)

Supramolecular Structure, Hirshfeld Surface Analysis, Morphological Study and DFT Calculations of the Triphenyltetrazolium Cobalt Thiocyanate Complex

The Formation, Structure, and Reactions of Binuclear Complexes of Cobalt

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