The series of cyanide‐bridged coordination polymers (P2)CuCNn (1), (P2)Cu{M(CN)2}n (M=Cu 3, Ag 4, Au 5) and molecular tetrametallic clusters {(P4)MM'(CN)}22+ (MM′=Cu2 6, Ag2 7, AgCu 8, AuCu 9, AuAg ...10) were obtained using the bidentate P2 and tetradentate P4 phosphane ligands (P2=1,2‐bis(diphenylphosphino)benzene; P4=tris(2‐diphenylphosphinophenyl)phosphane). All title complexes were crystallographically characterized to reveal a zig‐zag chain arrangement for 1 and 3–5, whereas 6–10 possess metallocyclic frameworks with different degree of metal‐metal bonding. The d10–d10 interactions were evaluated by the quantum theory of atoms in molecules (QTAIM) computational approach. The photophysical properties of 1–10 were investigated in the solid state and supported by theoretical analysis. The emission of compounds 1 and 3–5, dominated by metal‐to‐ligand charge transfer (MLCT) transitions located within {CuP2} motifs, is compatible with thermally activated delayed fluorescence (TADF) behaviour and a small energy gap between the T1 and S1 excited states. The luminescence characteristics of 6–10 are strongly dependent on the composition of the metal core; the emission band maxima vary in the range 484–650 nm with quantum efficiency reaching 0.56 (6). The origin of the emission for 6–8 and 10 at room temperature is assigned to delayed fluorescence. AuCu cluster 9, however, exhibits only phosphorescence that corresponds to theoretically predicted large value ΔE(S1−T1). DFT simulation highlights a crucial impact of metallophilic bonding on the nature and energy of the observed emission, the effect being greatly enhanced in the excited state.
The pronounced contraction of the metal–metal contacts in the excited state is a key factor in achieving tunable emission of d10 clusters without altering the ligand environment.
Abstract The series of cyanide‐bridged coordination polymers ( P 2 )CuCN n ( 1 ), ( P 2 )Cu{M(CN) 2 } n (M=Cu 3 , Ag 4 , Au 5 ) and molecular tetrametallic clusters {( P 4 )MM'(CN)} 2 2+ (MM′=Cu 2 6 ..., Ag 2 7 , AgCu 8 , AuCu 9 , AuAg 10 ) were obtained using the bidentate P 2 and tetradentate P 4 phosphane ligands ( P 2 =1,2‐bis(diphenylphosphino)benzene; P 4 =tris(2‐diphenylphosphinophenyl)phosphane). All title complexes were crystallographically characterized to reveal a zig‐zag chain arrangement for 1 and 3 – 5 , whereas 6 – 10 possess metallocyclic frameworks with different degree of metal‐metal bonding. The d 10 –d 10 interactions were evaluated by the quantum theory of atoms in molecules (QTAIM) computational approach. The photophysical properties of 1 – 10 were investigated in the solid state and supported by theoretical analysis. The emission of compounds 1 and 3 – 5 , dominated by metal‐to‐ligand charge transfer (MLCT) transitions located within {Cu P 2 } motifs, is compatible with thermally activated delayed fluorescence (TADF) behaviour and a small energy gap between the T 1 and S 1 excited states. The luminescence characteristics of 6 – 10 are strongly dependent on the composition of the metal core; the emission band maxima vary in the range 484–650 nm with quantum efficiency reaching 0.56 ( 6 ). The origin of the emission for 6 – 8 and 10 at room temperature is assigned to delayed fluorescence. AuCu cluster 9 , however, exhibits only phosphorescence that corresponds to theoretically predicted large value Δ E ( S 1 − T 1 ). DFT simulation highlights a crucial impact of metallophilic bonding on the nature and energy of the observed emission, the effect being greatly enhanced in the excited state.
A family of new branched phosphine derivatives {Ph2N–(C6H4) n −}3P → E (E = O 1–3, n = 1–3; E = S 4–6, n = 1–3; E = Se 7–9, n = 1–3; E = AuC6F5 4–6, n = 1–3), which are the donor–acceptor type ...molecules, exhibit efficient deep blue room temperature fluorescence (λem = 403–483 nm in CH2Cl2 solution, λem = 400–469 nm in the solid state). Fine tuning the emission characteristics can be achieved varying the length of aromatic oligophenylene bridge −(C6H4) n –. The pyramidal geometry of central R3P → E fragment on the one hand disrupts π-conjugation between the branches to preserve blue luminescence and high triplet energy, while on the other hand provides amorphous materials to prevent excimer formation and fluorescence self-quenching. Hence, compounds 2, 3, 5, and 12 were used as emitters to fabricate nondoped and doped electroluminescent devices. The luminophore 2 (E = O, n = 2) demonstrates excellently balanced bipolar charge transport and good nondoped device performance with a maximum external quantum efficiency (EQEmax) of 3.3% at 250 cd/m2 and Commission International de L’Eclairage (CIE) coordinates of (0.15, 0.08). The doped device of 3 (E = O, n = 3) shows higher efficiency (EQEmax of 6.5, 6.0 at 100 cd/m2) and high color purity with CIE (0.15, 0.06) that matches the HDTV standard blue. The time-resolved electroluminescence measurement indicates that high efficiency of the device can be attributed to the triplet–triplet annihilation to enhance generation of singlet excitons.
The series of cyanide-bridged coordination polymers (P
)CuCN
(1), (P
)Cu{M(CN)
}
(M=Cu 3, Ag 4, Au 5) and molecular tetrametallic clusters {(P
)MM'(CN)}
(MM'=Cu
6, Ag
7, AgCu 8, AuCu 9, AuAg 10) ...were obtained using the bidentate P
and tetradentate P
phosphane ligands (P
=1,2-bis(diphenylphosphino)benzene; P
=tris(2-diphenylphosphinophenyl)phosphane). All title complexes were crystallographically characterized to reveal a zig-zag chain arrangement for 1 and 3-5, whereas 6-10 possess metallocyclic frameworks with different degree of metal-metal bonding. The d
-d
interactions were evaluated by the quantum theory of atoms in molecules (QTAIM) computational approach. The photophysical properties of 1-10 were investigated in the solid state and supported by theoretical analysis. The emission of compounds 1 and 3-5, dominated by metal-to-ligand charge transfer (MLCT) transitions located within {CuP
} motifs, is compatible with thermally activated delayed fluorescence (TADF) behaviour and a small energy gap between the T
and S
excited states. The luminescence characteristics of 6-10 are strongly dependent on the composition of the metal core; the emission band maxima vary in the range 484-650 nm with quantum efficiency reaching 0.56 (6). The origin of the emission for 6-8 and 10 at room temperature is assigned to delayed fluorescence. AuCu cluster 9, however, exhibits only phosphorescence that corresponds to theoretically predicted large value ΔE(S
-T
). DFT simulation highlights a crucial impact of metallophilic bonding on the nature and energy of the observed emission, the effect being greatly enhanced in the excited state.
Development of genome editing methods created new opportunities for the development of etiology-based therapies of hereditary diseases. Here, we demonstrate that CRISPR/Cas9 can correct p.F508del ...mutation in the CFTR gene in the CFTE29o- cells and induced pluripotent stem cells (iPSCs) derived from patients with cystic fibrosis (CF). We used several combinations of Cas9, sgRNA and ssODN and measured editing efficiency in the endogenous CFTR gene and in the co-transfected plasmid containing the CFTR locus with the p.F508del mutation. The non-homologous end joining (NHEJ) frequency in the CFTR gene in the CFTE29o- cells varied from 1.25% to 2.54% of alleles. The best homology-directed repair (HDR) frequency in the endogenous CFTR locus was 1.42% of alleles. In iPSCs, the NHEJ frequency in the CFTR gene varied from 5.5% to 12.13% of alleles. The best HDR efficacy was 2.38% of alleles. Our results show that p.F508del mutation editing using CRISPR/Cas9 in CF patient-derived iPSCs is a relatively rare event and subsequent cell selection and cultivation should be carried out.
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