Abstract:New Mn(i)-based photoCORMs with a fac-{Mn(CO)3} moiety exhibit facile CO release upon simple exposure to light within the phototherapeutic region (no two photon excitation required).
“…The bond angle N(1)-Mn-O (4) = 78.3(1) , N(1)-Mn-C(2) = 171.1(2) and O(4)-Mn-C(3) = 174.5(2) deviate considerably from that of an ideal octahedral geometry. Among the three Mn-C (CO) bonds, the one trans to Br is the longest (1.840(7) Å) and subsequently the axial CO has the shortest bond length (1.05(1) Å), this is in agreement with those reported by Mascharak et al [40,43] The two CO groups trans to the azachalcone ligand have slightly different bond lengths. The CO which is trans to the N1 atom has a bond length of 1.131(6) Å while the one which is trans to O(4) is 1.140(6) Å.…”
Section: Structural Analysis Of 4chclsupporting
confidence: 89%
“…[ 25,35,39–42 ] Recently, Mascharak et al reported photoCORMs that have MLCTs in the 750‐ to 785‐nm range, the highest reported so far. [ 43 ] Among these, the complexes containing N and O as the chelating atoms such as acenaphthylen‐1‐one and quinolone‐8‐one exhibited MLCT at 630 and 785 nm, respectively. Thus, it can be concluded that even if the ligating atoms are same, the type of ligand framework can immensely affect the position of the MLCT.…”
A series of [Mn(CO)3(L)Br] complexes (1–5) are synthesized using azachalcones as ligands, wherein they are coordinated to the manganese metal through the nitrogen and oxygen donor atoms. Their characterization using various spectroscopic techniques, stability analysis in dimethyl sulfoxide solvent, photodecomposition analysis, and antiproliferative effect are reported herein. These complexes release CO upon exposure to green light radiation. DFT and TD‐DFT investigations are also reported to gather information regarding the electronic features of these complexes.
“…The bond angle N(1)-Mn-O (4) = 78.3(1) , N(1)-Mn-C(2) = 171.1(2) and O(4)-Mn-C(3) = 174.5(2) deviate considerably from that of an ideal octahedral geometry. Among the three Mn-C (CO) bonds, the one trans to Br is the longest (1.840(7) Å) and subsequently the axial CO has the shortest bond length (1.05(1) Å), this is in agreement with those reported by Mascharak et al [40,43] The two CO groups trans to the azachalcone ligand have slightly different bond lengths. The CO which is trans to the N1 atom has a bond length of 1.131(6) Å while the one which is trans to O(4) is 1.140(6) Å.…”
Section: Structural Analysis Of 4chclsupporting
confidence: 89%
“…[ 25,35,39–42 ] Recently, Mascharak et al reported photoCORMs that have MLCTs in the 750‐ to 785‐nm range, the highest reported so far. [ 43 ] Among these, the complexes containing N and O as the chelating atoms such as acenaphthylen‐1‐one and quinolone‐8‐one exhibited MLCT at 630 and 785 nm, respectively. Thus, it can be concluded that even if the ligating atoms are same, the type of ligand framework can immensely affect the position of the MLCT.…”
A series of [Mn(CO)3(L)Br] complexes (1–5) are synthesized using azachalcones as ligands, wherein they are coordinated to the manganese metal through the nitrogen and oxygen donor atoms. Their characterization using various spectroscopic techniques, stability analysis in dimethyl sulfoxide solvent, photodecomposition analysis, and antiproliferative effect are reported herein. These complexes release CO upon exposure to green light radiation. DFT and TD‐DFT investigations are also reported to gather information regarding the electronic features of these complexes.
“…One of the main challenges in designing an efficient photoCORM is activation by light in the phototherapeutic window (600–950 nm). To date, various strategies, including ancillary ligand modifications, , multiphoton excitation, , mixing with a triplet-state photosensitizer, quantum dots, upconverting nanoparticles, or as previously reported by our group, coupling with a visible light absorbing metal complex, and so forth, have been employed to activate the photo-CO dissociation under visible and NIR irradiation. Alternatively, the use of dye photosensitizers as light-harvesting components of the design allows for visible light-activated photoCORMs …”
Carbon monoxide (CO) is shown to enhance the sensitivity of cancer cells to generate reactive oxygen species such as singlet oxygen ( 1 O 2 ) from chemotherapeutics and reduce the drug resistance. Herein, we introduced two Mn-based photoactivated CO releasing molecules conjugated with an emissive BODIPY (BDP) moiety with a general formula of Mn(CO) 3 (bpy-R-BDP)Br (R = H or I), labeled as Mn-bpy-H-BDP and Mn-bpy-I-BDP. While both complexes release CO with visible light, Mn-bpy-I-BDP releases CO and produces 1 O 2 from a single molecule. In addition to 1 O 2 generation, iodination of BDP red shifts the absorption of Mn-bpy-I-BDP further into the visible region and significantly increases the dark stability of the complex. Cyclic voltammetry and density functional theory (DFT) calculations suggest a Mn-based highest occupied molecular orbital (HOMO) and a BDP-based lowest unoccupied molecular orbital (LUMO) in these complexes. However, time-dependent DFT calculations suggest that the HOMO − 2(π BDP ) → LUMO(π BDP * ) is the main optical transition upon excitation with visible light in both complexes. The presence of a phosphorescence peak from the triplet excited state of bpy-I-BDP in both the free ligand and its Mn complex at 77 K was used as additional evidence for 1 O 2 production. We also probed formation of photo-intermediates and products during photolysis with Fourier-transform infrared, 1 H NMR, emission, and absorption experiments and DFT calculations.
“…In a similar manner, carbon monoxide (CO), although mostly known for its strong toxicity due to strong binding to hemoglobine, was recently discovered to be produced endogenously in small amounts and responsible, similarly to NO, for a variety of physiological effects [19] . This has also triggered the development of targeted CO photoreleasing compounds ( photoCORMs ) [20–27] …”
Section: Introductionmentioning
confidence: 99%
“… [19] This has also triggered the development of targeted CO photoreleasing compounds ( photoCORMs ). [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ]…”
A density matrix renormalization group‐self consistent field (DMRG‐SCF) study has been carried out to calculate the low‐lying excited states of CpMo(CO)2NO, a molybdenum complex containing NO and CO ligands. In order to automatically select an appropriate active space, a novel procedure employing the maximum single‐orbital entropy for several states has been introduced and shown to be efficient and easy‐to‐implement when several electronic states are simultaneously considered. The analysis of the resulting natural transition orbitals and charge‐transfer numbers shows that the lowest five excited electronic states are excitation into metal‐NO antibonding orbitals, which offer the possibility for nitric oxide (NO) photorelease after excitation with visible light. Higher excited states are metal‐centered excitations with contributions of metal‐CO antibonding orbitals, which may serve as a gateway for carbon monoxide (CO) delivery. Time‐dependent density functional theory calculations done for comparison, show that the state characters agree remarkably well with those from DMRG‐SCF, while excitation energies are 0.4–1.0 eV red‐shifted with respect to the DMRG‐SCF ones.
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