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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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

Název v anglickém jazyce

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

Popis výsledku anglicky

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

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

—

Projekt

<a href="/cs/project/ME10124" target="_blank" >ME10124: Fotoindukovaná seperace náboje v metaloproteinových systémech: Teorie a experiment</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2012

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

134

Číslo periodika v rámci svazku

34

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

14201-14207

Kód UT WoS článku

000308043400044

EID výsledku v databázi Scopus

—