TY - JOUR
T1 - Heteroleptic platinum(ii) isocyanide complexes
T2 - Convenient synthetic access, polymorphs, and vapoluminescence
AU - Janzen, Daron E.
AU - Mann, Kent R.
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2015.
PY - 2015/3/7
Y1 - 2015/3/7
N2 - A convenient synthetic scheme was developed to access a series of square-planar Pt(ii) complexes of the form (TBA)[Pt(CN)3(CNR)] (TBA = tetra-n-butyl ammonium cation, R = CH3, c-C6H11, p-(C2H5)-C6H4). These heteroleptic complexes were characterized by combustion analyses, single-crystal X-ray structure determinations, HRFAB-MS, 1H NMR, ATR-IR, solution UV-Vis, and solid-state emission spectroscopies. Surprisingly, each of these complexes exhibit low energy room temperature solid-state luminescence in the absence of intermolecular Pt-Pt interactions. Additionally, the polymorphic behavior of (TBA)[Pt(CN)3(CN-c-C6H11)] was elucidated through a combination of single-crystal X-ray structure determinations, X-ray powder diffraction, and mass uptake experiments. Vapoluminescence and polymorphic transformations of (TBA)[Pt(CN)3(CN-c-C6H11)] were concomitant with water vapor absorption. A new double-salt complex [Pt(terpy)Cl] [Pt(CN)3(CNCH3)] (terpy = 2,2′,6′,2′′-terpyridine) was also synthesized and characterized by combustion analysis, ATR-IR, HRFAB-MS, and solid-state UV-Vis and emission spectroscopies. The vapoluminescent properties of this salt in response to water were examined by mass uptake experiments, ATR-IR, and solid-state emission spectroscopy. A principal component analysis (PCA) of the solid-state emission changes induced by water vapor confirmed the presence of an intermediate emissive species.
AB - A convenient synthetic scheme was developed to access a series of square-planar Pt(ii) complexes of the form (TBA)[Pt(CN)3(CNR)] (TBA = tetra-n-butyl ammonium cation, R = CH3, c-C6H11, p-(C2H5)-C6H4). These heteroleptic complexes were characterized by combustion analyses, single-crystal X-ray structure determinations, HRFAB-MS, 1H NMR, ATR-IR, solution UV-Vis, and solid-state emission spectroscopies. Surprisingly, each of these complexes exhibit low energy room temperature solid-state luminescence in the absence of intermolecular Pt-Pt interactions. Additionally, the polymorphic behavior of (TBA)[Pt(CN)3(CN-c-C6H11)] was elucidated through a combination of single-crystal X-ray structure determinations, X-ray powder diffraction, and mass uptake experiments. Vapoluminescence and polymorphic transformations of (TBA)[Pt(CN)3(CN-c-C6H11)] were concomitant with water vapor absorption. A new double-salt complex [Pt(terpy)Cl] [Pt(CN)3(CNCH3)] (terpy = 2,2′,6′,2′′-terpyridine) was also synthesized and characterized by combustion analysis, ATR-IR, HRFAB-MS, and solid-state UV-Vis and emission spectroscopies. The vapoluminescent properties of this salt in response to water were examined by mass uptake experiments, ATR-IR, and solid-state emission spectroscopy. A principal component analysis (PCA) of the solid-state emission changes induced by water vapor confirmed the presence of an intermediate emissive species.
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U2 - 10.1039/c4dt03820g
DO - 10.1039/c4dt03820g
M3 - Article
C2 - 25626923
AN - SCOPUS:84923368824
SN - 1477-9226
VL - 44
SP - 4223
EP - 4237
JO - Dalton Transactions
JF - Dalton Transactions
IS - 9
ER -