Thermally Tunable Dual Emission of the d8–d8 Dimer [Pt2(μ-P2O5(BF2)2)4]4–
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Thermally Tunable Dual Emission of the d8–d8 Dimer [Pt2(μ-P2O5(BF2)2)4]4–
Original language description
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
Czech name
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Czech description
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Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2016
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
55
Issue of the periodical within the volume
5
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
2441-2449
UT code for WoS article
000371753500055
EID of the result in the Scopus database
2-s2.0-84960359244