Structural Control of (1)A(2u)-to-(3)A(2u) Intersystem Crossing in Diplatinum(II,II) Complexes

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F12%3A00384550" target="_blank" >RIV/61388955:_____/12:00384550 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/ja305666b" target="_blank" >http://dx.doi.org/10.1021/ja305666b</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/ja305666b" target="_blank" >10.1021/ja305666b</a>

Result language
angličtina
Original language name
Structural Control of (1)A(2u)-to-(3)A(2u) Intersystem Crossing in Diplatinum(II,II) Complexes
Original language description
Analysis of variable-temperature fluorescence quantum yield and lifetime data for per(difluoroboro)tetrakis(pyrophosphito)diplatinate(II) ([Pt-2(mu-P2O5(BF2)(2))(4))(4-), abbreviated Pt(pop-BF2)), yields a radiative decay rate (k(r) = 1.7 X 10(8) s(-1))an order of magnitude greater than that of the parent complex, Pt(pop). Its temperature-independent and activated intersystem crossing (ISC) pathways are at least 18 and 142 times slower than those of Pt(pop) [ISC activation energies: 2230 cm(-1) for Pt(pop-BF2); 1190 cm(-1) for Pt(pop)]. The slowdown in the temperature-independent ISC channel is attributed to two factors: (1) reduced spin-orbit coupling between the (1)A(2u) state and the mediating triplet(s), owing to increases of LMCT energies relative to the excited singlet; and (2) diminished access to solvent, which for Pt(pop) facilitates dissipation of the excess energy into solvent vibrational modes. The dramatic increase in E-a is attributed to increased P-O-P framework rigidit
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Project
<a href="/en/project/ME10124" target="_blank" >ME10124: Photoinduced Charge Separation in Metalloprotein-Based Systems: Theory and Experiment</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2012
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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