Thermally Tunable Dual Emission of the d8–d8 Dimer [Pt2(μ-P2O5(BF2)2)4]4–

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F16%3A00457999" target="_blank" >RIV/61388955:_____/16:00457999 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5b02839" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.5b02839</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5b02839" target="_blank" >10.1021/acs.inorgchem.5b02839</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermally Tunable Dual Emission of the d8–d8 Dimer [Pt2(μ-P2O5(BF2)2)4]4–

Popis výsledku v původním jazyce

High-resolution fluorescence, phosphorescence, as well as related excitation spectra, and, in particular, the emission decay behavior of solid [Bu4N]4[Pt2(μ-P2O5(BF2)2)4], abbreviated Pt(pop-BF2), have been investigated over a wide temperature range, 1.3–310 K. We focus on the lowest excited states that result from dσ*pσ (5dz2–6pz) excitations, i.e., the singlet state S1 (of 1A2u symmetry in D4h) and the lowest triplet T1, which splits into spin–orbit substates A1u(3A2u) and Eu(3A2u). After optical excitation, an unusually slow intersystem crossing (ISC) is observed. As a consequence, the compound shows efficient dual emission, consisting of blue fluorescence and green phosphorescence with an overall emission quantum yield of ∼100% over the investigated temperature range. Our investigation sheds light on this extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in Pt(pop-BF2) are largely forbidden due to spin-, symmetry-, and Franck–Condon overlap-restrictions and, therefore, the ISC time is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow, are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime also is temperature-dependent, reflecting the relative population of the triplet T1 substates Eu and A1u. The highly resolved phosphorescence shows a ∼220 cm–1 red shift below 10 K, attributable to zero-field splitting of 40 cm–1 plus a promoting vibration of 180 cm–1.n

Název v anglickém jazyce

Thermally Tunable Dual Emission of the d8–d8 Dimer [Pt2(μ-P2O5(BF2)2)4]4–

Popis výsledku anglicky

High-resolution fluorescence, phosphorescence, as well as related excitation spectra, and, in particular, the emission decay behavior of solid [Bu4N]4[Pt2(μ-P2O5(BF2)2)4], abbreviated Pt(pop-BF2), have been investigated over a wide temperature range, 1.3–310 K. We focus on the lowest excited states that result from dσ*pσ (5dz2–6pz) excitations, i.e., the singlet state S1 (of 1A2u symmetry in D4h) and the lowest triplet T1, which splits into spin–orbit substates A1u(3A2u) and Eu(3A2u). After optical excitation, an unusually slow intersystem crossing (ISC) is observed. As a consequence, the compound shows efficient dual emission, consisting of blue fluorescence and green phosphorescence with an overall emission quantum yield of ∼100% over the investigated temperature range. Our investigation sheds light on this extraordinary dual emission behavior, which is unique for a heavy-atom transition metal compound. Direct ISC processes in Pt(pop-BF2) are largely forbidden due to spin-, symmetry-, and Franck–Condon overlap-restrictions and, therefore, the ISC time is as long as 29 ns for T < 100 K. With temperature increase, two different thermally activated pathways, albeit still relatively slow, are promoted by spin-vibronic and vibronic mechanisms, respectively. Thus, distinct temperature dependence of the ISC processes results and, as a consequence, also of the fluorescence/phosphorescence intensity ratio. The phosphorescence lifetime also is temperature-dependent, reflecting the relative population of the triplet T1 substates Eu and A1u. The highly resolved phosphorescence shows a ∼220 cm–1 red shift below 10 K, attributable to zero-field splitting of 40 cm–1 plus a promoting vibration of 180 cm–1.n

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

55

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

2441-2449

Kód UT WoS článku

000371753500055

EID výsledku v databázi Scopus

2-s2.0-84960359244