PMID- 26641121
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20151209
LR  - 20151208
IS  - 1549-9618 (Print)
IS  - 1549-9618 (Linking)
VI  - 1
IP  - 1
DP  - 2005 Jan
TI  - Computational and Spectroscopic Studies of Re(I) Bipyridyl Complexes Containing 
      2,6-Dimethylphenylisocyanide (CNx) Ligand.
PG  - 95-106
LID - 10.1021/ct049956g [doi]
AB  - Density Functional Theory (DFT) calculations produce optimized geometries of the 
      complexes [Re(CO)3(bpy)Cl] (1), [Re(CO)3(bpy)(py)](CF3SO3) (2), 
      [Re(CO)3(bpy)(CNx)](CF3SO3) (3), and [Re(CO)(bpy)(CNx)3](CF3SO3) (4), where bpy = 
      2,2'-bipyridine, py = pyridine, and CNx = 2,6-dimethylphenylisocyanide in their 
      ground and lowest-lying triplet states. The ground-state optimized geometry for 
      the cation of [Re(CO)3(bpy)(CNx)](CF3SO3) (3) results in a Re-C (CNx) bond length 
      of 2.10 A, a Re-C (CO) bond length trans to CNx of 2.01 A, and a Re-C (CO) bond 
      length cis to CNx of 1.96 A which compares favorably to the single-crystal 
      analysis of a Re-C (CNx) bond length of 2.074(4) A, a Re-C (CO) bond length trans 
      to CNx of 1.971(4) A, and Re-C (CO) bond length cis to CNx of 1.932(4) A. The 
      majority of the singlet excited-state energies calculated using Time-dependent 
      Density Functional Theory (TDDFT) and Conductor-like Polarizable Continuum Model 
      (CPCM) are metal-ligand-to-ligand charge transfer (MLLCT) states and are in good 
      agreement with the UV-vis spectral energies for the complexes in ethanol. The 
      complexes exhibit emission both at room temperature and at 77 K except 4 which is 
      only emissive at 77 K. The 77 K emission lifetimes range from 3.9 mus for 1 to 8.8 
      mus for 3. The emissive lowest-lying triplet state is a (3)MLLCT state for 
      complexes 1-3 but a triplet ligand-to-metal charge transfer ((3)LMCT) state for 
      complex 4. The electronic, electrochemical, thermodynamic, HOMO-LUMO, and 
      emitting-state energy gaps as well as the emission lifetimes increase in the 
      order 1 < 2 < 3. A (3)d-d excited- state, which is located above the (3)LMCT 
      state, accounts for the loss of room-temperature emission for complex 4.
FAU - Stoyanov, Stanislav R
AU  - Stoyanov SR
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
FAU - Villegas, John M
AU  - Villegas JM
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
FAU - Cruz, Arvin J
AU  - Cruz AJ
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
FAU - Lockyear, Loranelle L
AU  - Lockyear LL
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
FAU - Reibenspies, Joseph H
AU  - Reibenspies JH
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
FAU - Rillema, D Paul
AU  - Rillema DP
AD  - Department of Chemistry, Wichita State University, 1845 N. Fairmount Street, 
      Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 N. 
      First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A 
      & M University, P.O. Box 30012, College Station, Texas 77842-3012.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Theory Comput
JT  - Journal of chemical theory and computation
JID - 101232704
EDAT- 2005/01/01 00:00
MHDA- 2005/01/01 00:01
CRDT- 2015/12/08 06:00
PHST- 2015/12/08 06:00 [entrez]
PHST- 2005/01/01 00:00 [pubmed]
PHST- 2005/01/01 00:01 [medline]
AID - 10.1021/ct049956g [doi]
PST - ppublish
SO  - J Chem Theory Comput. 2005 Jan;1(1):95-106. doi: 10.1021/ct049956g.