TY - JOUR
T1 - Switchable ambient-temperature singlet-triplet dual emission in nonconjugated donor-acceptor triarylboron-Pt complexes
AU - Hudson, Zachary M.
AU - Zhao, Shu Bin
AU - Wang, Rui Yao
AU - Wang, Suning
PY - 2009/6/15
Y1 - 2009/6/15
N2 - A triarylboron compound SiBNPA (1) containing a BMes2 acceptor and an N-(2'-pyridyl)-7-azaindolyl (NPA) donor linked by a tetrahedral silane group has been synthesised. This molecule displays unusual white singlet-triplet dual emission at 77 K, with an exceptionally long phosphorescent decay time (2.2 s). Fluoride titration experiments established that the singlet and triplet emission peaks are due to acceptor-based Mes -> charge transfer and donor-based 3π-> π transitions, respectively. This dual emission was found to be persistent and observable at ambient temperature in its PtII complex [Pt(N,n-Si-BNPA)Ph2] (2a). Furthermore, 2a was found to undergo intramolecular "roll-over" C-H activation to produce the N,C-chelate com-plex [Pt(N,C-Si-BNPA)(SMe2)Ph] (2b). This compound also displays ambient temperature singlet-triplet dual emission, but with a much greater phosphorescent efficiency than 2 a due to the formation of a more stable chelate ring. Addition of fluoride was found to have little impact on the phosphorescent emission of 2a, but resulted in a large enhancement of the phosphorescent emission intensity of 2b. To establish the impact of donor-acceptor geometry on this singlet-triplet dual emission, the properties of linearly conjugated donor-acceptor complexes [Pt-(N,N-BNPA)Ph2] (3a) and [Pt(N,CBNPA)Ph2] (3b) were also examined. Consistent with 2a and 2b, the N,Cchelate complex 3b has a much higher phosphorescent efficiency than the N,N-chelate 3a. Although 3a and 3b show bright and fluoride-switchable phosphorescence at ambient temperature, they are not dual emissive and show only metal-to-ligand chage-transfer-based phosphorescence. The nonconjugated donor-acceptor geometry and the overlap of the donor and acceptor singlet and triplet excitation bands in Si-BNPA and its PtII complexes may thus be the key for achieving singlet-triplet dual emission on two separated chromophores in a single molecule.
AB - A triarylboron compound SiBNPA (1) containing a BMes2 acceptor and an N-(2'-pyridyl)-7-azaindolyl (NPA) donor linked by a tetrahedral silane group has been synthesised. This molecule displays unusual white singlet-triplet dual emission at 77 K, with an exceptionally long phosphorescent decay time (2.2 s). Fluoride titration experiments established that the singlet and triplet emission peaks are due to acceptor-based Mes -> charge transfer and donor-based 3π-> π transitions, respectively. This dual emission was found to be persistent and observable at ambient temperature in its PtII complex [Pt(N,n-Si-BNPA)Ph2] (2a). Furthermore, 2a was found to undergo intramolecular "roll-over" C-H activation to produce the N,C-chelate com-plex [Pt(N,C-Si-BNPA)(SMe2)Ph] (2b). This compound also displays ambient temperature singlet-triplet dual emission, but with a much greater phosphorescent efficiency than 2 a due to the formation of a more stable chelate ring. Addition of fluoride was found to have little impact on the phosphorescent emission of 2a, but resulted in a large enhancement of the phosphorescent emission intensity of 2b. To establish the impact of donor-acceptor geometry on this singlet-triplet dual emission, the properties of linearly conjugated donor-acceptor complexes [Pt-(N,N-BNPA)Ph2] (3a) and [Pt(N,CBNPA)Ph2] (3b) were also examined. Consistent with 2a and 2b, the N,Cchelate complex 3b has a much higher phosphorescent efficiency than the N,N-chelate 3a. Although 3a and 3b show bright and fluoride-switchable phosphorescence at ambient temperature, they are not dual emissive and show only metal-to-ligand chage-transfer-based phosphorescence. The nonconjugated donor-acceptor geometry and the overlap of the donor and acceptor singlet and triplet excitation bands in Si-BNPA and its PtII complexes may thus be the key for achieving singlet-triplet dual emission on two separated chromophores in a single molecule.
KW - Boron cyclometalation
KW - Donor-acceptor systems
KW - Fluorescence
KW - Platinum
UR - http://www.scopus.com/inward/record.url?scp=66749123580&partnerID=8YFLogxK
U2 - 10.1002/chem.200900641
DO - 10.1002/chem.200900641
M3 - Article
AN - SCOPUS:66749123580
SN - 0947-6539
VL - 15
SP - 6131
EP - 6137
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 25
ER -