Photophysics of singlet and triplet intraligand excited states in [ReCl(CO)3(1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes

Excited-state characters and dynamics of [ReCl(CO)3(3-R-1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes (abbreviated ReGV-R, R = CH3, Ph, PhBu(t), PhCF3, PhNO2, PhNMe2) were investigated by pico- and nanosecond time-resolved infrared spectroscopy (TRIR) and excited-state DFT and TD-DFT calculations...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 136; no. 16; p. 5963
Main Authors: Blanco-Rodríguez, Ana María, Kvapilová, Hana, Sýkora, Jan, Towrie, Michael, Nervi, Carlo, Volpi, Giorgio, Záliš, Stanislav, Vlček, Jr, Antonín
Format: Journal Article
Language:English
Published: United States 23.04.2014
ISSN:1520-5126
Online Access:Get more information
Tags: Add Tag
No Tags, Be the first to tag this record!
Abstract Excited-state characters and dynamics of [ReCl(CO)3(3-R-1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes (abbreviated ReGV-R, R = CH3, Ph, PhBu(t), PhCF3, PhNO2, PhNMe2) were investigated by pico- and nanosecond time-resolved infrared spectroscopy (TRIR) and excited-state DFT and TD-DFT calculations. Near UV excitation populates the lowest singlet state S1 that undergoes picosecond intersystem crossing (ISC) to the lowest triplet T1. Both states are initially formed hot and relax with ∼20 ps lifetime. TRIR together with quantum chemical calculations reveal that S1 is predominantly a ππ* state localized at the 1-(2-pyridyl)-imidazo[1,5-α]pyridine (= impy) ligand core, with impy → PhNO2 and PhNMe2 → impy intraligand charge-transfer contributions in the case of ReGV-PhNO2 and ReGV-PhNMe2, respectively. T1 is predominantly ππ*(impy) in all cases. It follows that excited singlet and corresponding triplet states have to some extent different characters and structures even if originating nominally from the same preponderant one-electron excitations. ISC occurs with a solvent-independent (CH2Cl2, MeCN) 20-30 ps lifetime, except for ReGV-PhNMe2 (10 ps in CH2Cl2, 100 ps in MeCN). ISC is 200-300 times slower than in analogous complexes with low-lying MLCT states. This difference is interpreted in terms of spin-orbit interaction and characters of orbitals involved in one-electron excitations that give rise to S1 and T1 states. ReGV-R present a unique case of octahedral heavy-metal complexes where the S1 lifetime is long enough to allow for separate spectroscopic characterization of singlet and triplet excited states. This study provides an insight into dynamics and intersystem crossing pathways of low-lying singlet and triplet excited states localized at bidentate ligands bound directly to a heavy metal atom. Rather long (1)IL lifetimes indicate the possibility of photonic applications of singlet excited states.
AbstractList Excited-state characters and dynamics of [ReCl(CO)3(3-R-1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes (abbreviated ReGV-R, R = CH3, Ph, PhBu(t), PhCF3, PhNO2, PhNMe2) were investigated by pico- and nanosecond time-resolved infrared spectroscopy (TRIR) and excited-state DFT and TD-DFT calculations. Near UV excitation populates the lowest singlet state S1 that undergoes picosecond intersystem crossing (ISC) to the lowest triplet T1. Both states are initially formed hot and relax with ∼20 ps lifetime. TRIR together with quantum chemical calculations reveal that S1 is predominantly a ππ* state localized at the 1-(2-pyridyl)-imidazo[1,5-α]pyridine (= impy) ligand core, with impy → PhNO2 and PhNMe2 → impy intraligand charge-transfer contributions in the case of ReGV-PhNO2 and ReGV-PhNMe2, respectively. T1 is predominantly ππ*(impy) in all cases. It follows that excited singlet and corresponding triplet states have to some extent different characters and structures even if originating nominally from the same preponderant one-electron excitations. ISC occurs with a solvent-independent (CH2Cl2, MeCN) 20-30 ps lifetime, except for ReGV-PhNMe2 (10 ps in CH2Cl2, 100 ps in MeCN). ISC is 200-300 times slower than in analogous complexes with low-lying MLCT states. This difference is interpreted in terms of spin-orbit interaction and characters of orbitals involved in one-electron excitations that give rise to S1 and T1 states. ReGV-R present a unique case of octahedral heavy-metal complexes where the S1 lifetime is long enough to allow for separate spectroscopic characterization of singlet and triplet excited states. This study provides an insight into dynamics and intersystem crossing pathways of low-lying singlet and triplet excited states localized at bidentate ligands bound directly to a heavy metal atom. Rather long (1)IL lifetimes indicate the possibility of photonic applications of singlet excited states.
Author Záliš, Stanislav
Vlček, Jr, Antonín
Nervi, Carlo
Kvapilová, Hana
Blanco-Rodríguez, Ana María
Sýkora, Jan
Volpi, Giorgio
Towrie, Michael
Author_xml – sequence: 1
  givenname: Ana María
  surname: Blanco-Rodríguez
  fullname: Blanco-Rodríguez, Ana María
  organization: School of Biological and Chemical Sciences, Queen Mary University of London , Mile End Road, London E1 4NS, United Kingdom
– sequence: 2
  givenname: Hana
  surname: Kvapilová
  fullname: Kvapilová, Hana
– sequence: 3
  givenname: Jan
  surname: Sýkora
  fullname: Sýkora, Jan
– sequence: 4
  givenname: Michael
  surname: Towrie
  fullname: Towrie, Michael
– sequence: 5
  givenname: Carlo
  surname: Nervi
  fullname: Nervi, Carlo
– sequence: 6
  givenname: Giorgio
  surname: Volpi
  fullname: Volpi, Giorgio
– sequence: 7
  givenname: Stanislav
  surname: Záliš
  fullname: Záliš, Stanislav
– sequence: 8
  givenname: Antonín
  surname: Vlček, Jr
  fullname: Vlček, Jr, Antonín
BackLink https://www.ncbi.nlm.nih.gov/pubmed/24669762$$D View this record in MEDLINE/PubMed
BookMark eNo1kMtKAzEYhYMo9qILX0CybMFoLjOZzFIGbyBURFellGT-TJsyNyYROi58J1_EZ7L1sjqH78C3OCN0WDe1ReiM0UtGObva6IgJmqrqAA1ZzCmJGZcDNPJ-QymNuGLHaMAjKdNE8iH6eFo3oWnXvXe5x02BvatXpQ1Y14BD59p9d3XodOlWe2a3uQsWsA86WL-b8PzZZuUkm03FhJEJJ23fOejLKXGVA_3ezNlFTL4-Fz_c1Xa6wHlT7cRb60_QUaFLb0__coxeb29esnvyOLt7yK4fiRaKBcJBqNQYKQoNNNEcZAJGMgWFyS2oCApqEk0BChVbAcBMJDRLmFY8T2nO-Rid_3rbN1NZWLadq3TXL_-P4N_oImFr
CitedBy_id crossref_primary_10_1016_j_jphotochem_2022_114477
crossref_primary_10_1016_j_molstruc_2021_132175
crossref_primary_10_1039_C9RA10848C
crossref_primary_10_1021_jacs_7b12868
crossref_primary_10_1007_s11224_021_01756_4
crossref_primary_10_1016_j_aca_2017_09_016
crossref_primary_10_1016_j_dyepig_2018_07_036
crossref_primary_10_1080_00397911_2019_1650188
crossref_primary_10_3390_molecules28093703
crossref_primary_10_3390_molecules29112668
crossref_primary_10_1002_ajoc_202200171
crossref_primary_10_1002_chem_202102837
crossref_primary_10_1016_j_dyepig_2017_04_034
crossref_primary_10_1016_j_jscs_2014_12_009
crossref_primary_10_3390_molecules26237161
crossref_primary_10_1002_ange_201916381
crossref_primary_10_1016_j_ccr_2020_213755
crossref_primary_10_1016_j_dyepig_2021_109455
crossref_primary_10_1039_c4pp00301b
crossref_primary_10_1002_cptc_202000307
crossref_primary_10_1016_j_ccr_2016_04_007
crossref_primary_10_1016_j_molstruc_2025_143717
crossref_primary_10_1002_ejic_201403053
crossref_primary_10_1016_j_jphotochem_2024_116256
crossref_primary_10_3390_molecules29030653
crossref_primary_10_1007_s00894_023_05712_3
crossref_primary_10_1039_D2RA04874D
crossref_primary_10_1016_j_ccr_2017_01_008
crossref_primary_10_1002_ejic_201402912
crossref_primary_10_1080_03067319_2019_1676422
crossref_primary_10_3390_chemistry3030050
crossref_primary_10_1016_j_jorganchem_2015_05_045
crossref_primary_10_1002_anie_201916381
crossref_primary_10_1016_j_jphotochem_2021_113714
crossref_primary_10_1016_j_ica_2020_119662
crossref_primary_10_1016_j_poly_2017_11_048
crossref_primary_10_1016_j_dyepig_2015_12_005
crossref_primary_10_1016_j_poly_2015_02_005
ContentType Journal Article
DBID NPM
DOI 10.1021/ja413098m
DatabaseName PubMed
DatabaseTitle PubMed
DatabaseTitleList PubMed
Database_xml – sequence: 1
  dbid: NPM
  name: PubMed
  url: http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed
  sourceTypes: Index Database
DeliveryMethod no_fulltext_linktorsrc
Discipline Chemistry
EISSN 1520-5126
ExternalDocumentID 24669762
Genre Journal Article
GroupedDBID ---
-DZ
-ET
-~X
.DC
.K2
4.4
53G
55A
5GY
5RE
5VS
7~N
85S
AABXI
AAHBH
AAYWT
ABBLG
ABJNI
ABLBI
ABMVS
ABPPZ
ABQRX
ABUCX
ACBEA
ACGFO
ACGFS
ACJ
ACNCT
ACS
ADHLV
AEESW
AENEX
AETEA
AFEFF
AGXLV
AHDLI
AHGAQ
ALMA_UNASSIGNED_HOLDINGS
AQSVZ
BAANH
BKOMP
CS3
CUPRZ
DU5
EBS
ED~
EJD
F5P
GGK
GNL
IH2
IH9
JG~
LG6
NPM
P2P
ROL
RXW
TAE
TN5
UHB
UI2
UKR
UPT
VF5
VG9
W1F
WH7
XSW
YQT
YZZ
ZCA
~02
ID FETCH-LOGICAL-a381t-2d389bb63fad07a2d67db618dfbced84df0b7a0ddf85e3dd1b43a171a82c90c22
ISICitedReferencesCount 67
ISICitedReferencesURI http://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestLinkType=CitingArticles&DestApp=WOS_CPL&KeyUT=000335086100032&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D
IngestDate Mon Jul 21 06:07:33 EDT 2025
IsPeerReviewed true
IsScholarly true
Issue 16
Language English
LinkModel OpenURL
MergedId FETCHMERGED-LOGICAL-a381t-2d389bb63fad07a2d67db618dfbced84df0b7a0ddf85e3dd1b43a171a82c90c22
PMID 24669762
ParticipantIDs pubmed_primary_24669762
PublicationCentury 2000
PublicationDate 2014-04-23
PublicationDateYYYYMMDD 2014-04-23
PublicationDate_xml – month: 04
  year: 2014
  text: 2014-04-23
  day: 23
PublicationDecade 2010
PublicationPlace United States
PublicationPlace_xml – name: United States
PublicationTitle Journal of the American Chemical Society
PublicationTitleAlternate J Am Chem Soc
PublicationYear 2014
SSID ssj0004281
Score 2.3922527
Snippet Excited-state characters and dynamics of [ReCl(CO)3(3-R-1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes (abbreviated ReGV-R, R = CH3, Ph, PhBu(t), PhCF3,...
SourceID pubmed
SourceType Index Database
StartPage 5963
Title Photophysics of singlet and triplet intraligand excited states in [ReCl(CO)3(1-(2-pyridyl)-imidazo[1,5-α]pyridine)] complexes
URI https://www.ncbi.nlm.nih.gov/pubmed/24669762
Volume 136
WOSCitedRecordID wos000335086100032&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D
hasFullText
inHoldings 1
isFullTextHit
isPrint
link http://cvtisr.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwtV1Lb9NAEF6lgAQXxJvy0h6IlAi28vq5PrZOERIorUqRKlVVtfbuFquJHYUQUg78J_4IPwkx-7BrWoHgwGXlzKyjaOfLzHg8D4See6yQgUoVEYwVJBQJh7-Up4hUUVCknPNEmT6zb5PxmB0cpLu93o-mFmY5SaqKrVbp7L-KGmggbF06-w_ibr8UCHANQocVxA7rXwl-90OtmwXo4zdpGjoYMJE2kXwx13F1PRXABDhONE2uCuN2mtIikx3bj7b2ZDbR73d3-r7uA8UogcUns7N5Kc6Ak5JyWgr-pYa9oAuziPSz7T5cRiOzx7YvhU82Z12uXKriZTe4U9pSvWjbF7hk0jZYMAFw1mSvFvbN_ujkk418b1ZclxtZYmth3iz5rJzUS0OmxrryquW-0-St0Wk9d3nC57nI9Wc3XqxbTeBiItSk0tiy5Q3p9Dg8FYMvE_-i6G2rlQbRXb0dpVbNXjIo4AKZQQba1qds2t0DYp9NDYj8MI5TZ1X-zL3Q27thraG1JNZmZaxjTU1VLwi36YXl6z5Z7jfo_tXuvgvPQsYn2r-Fbjop4k0LwtuoJ6s76HrWzBC8i752wYhrhR0YMQAPOzDiDhixAyO2YAQWPtRQHGQ7w2BAyaCF4LAB4CF9GZHv344a2A2PcAu5e-j9q-397DVxEz8IB89xQXwB_nOex4Hiwku4L-JE5DFlQuWFFCwUyssT7gmhWCQDIWgeBpwmlDO_SL3C9--jK1VdyYcIg-qBA6MyAAMUxoJyWYQpgztkSPMkFuvogT2645lt63LcHOqj33IeoxvnaHuCripQGfIpulYsF-XH-TMjvp8ag46P
linkProvider National Library of Medicine
openUrl ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Photophysics+of+singlet+and+triplet+intraligand+excited+states+in+%5BReCl%28CO%293%281-%282-pyridyl%29-imidazo%5B1%2C5-%CE%B1%5Dpyridine%29%5D+complexes&rft.jtitle=Journal+of+the+American+Chemical+Society&rft.au=Blanco-Rodr%C3%ADguez%2C+Ana+Mar%C3%ADa&rft.au=Kvapilov%C3%A1%2C+Hana&rft.au=S%C3%BDkora%2C+Jan&rft.au=Towrie%2C+Michael&rft.date=2014-04-23&rft.eissn=1520-5126&rft.volume=136&rft.issue=16&rft.spage=5963&rft_id=info:doi/10.1021%2Fja413098m&rft_id=info%3Apmid%2F24669762&rft_id=info%3Apmid%2F24669762&rft.externalDocID=24669762