Synthesis and structures of photoactive manganese–carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzothiazole and 2-(quinolin-2-yl)-1,3-benzothiazole

Stenger-Smith, Jenny; Chakraborty, Indranil; Carrington, Samantha J.; Mascharak, Pradip K.

doi:10.1107/s2053229617004429

Cited by 5 publications

(3 citation statements)

References 14 publications

(16 reference statements)

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“…Transition metal complexes that can photochemically release carbon monoxide upon exposure to visible light have been reported recently (Chakraborty et al, 2014;Stenger-Smith et al, 2017). Facile release of carbon monoxide has been observed in manganese carbonyls containing acenaphthalene derivatives (Carrington et al, 2015) including the ligand MIAN {2-[(4-chlorophenyl)imino]acenapthylen-1-one}, the subject of this study, shown in the Scheme.…”

Section: Chemical Contextmentioning

confidence: 90%

A temperature-dependent phase transformation of (E)-2-[(4-chlorophenyl)imino]acenaphthylen-1-one

Bao

Olmstead

2017

Acta Cryst E

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The crystal structure determination based on 90 K data of the title imine ligand, C 18 H 10 ClNO, revealed non-merohedral twinning with three twin domains. In our experience, this is an indication of an ordering phase transition. Consequently, the structure was redetermined with higher temperature data, and a reversible phase transition was discovered. The higher temperature phase is indeed an ordered structure. At the higher temperature, the 4-chlorophenyl group has rotated by ca 7 into a crystallographic mirror plane. Warming the crystal from 90 K to 250 K changes the space group from triclinic P1, to monoclinic P2 1 /m. Diverse non-classical interactions are present in the crystal packing, and these are described for the phase change reported in this work. The crystal structure of the title imine ligand, measured at 100 K, has been reported on previously [Kovach et al. (2011). J. Mol. Struct. 992, 33-38]. Chemical contextTransition metal complexes that can photochemically release carbon monoxide upon exposure to visible light have been reported recently (Chakraborty et al., 2014;Stenger-Smith et al., 2017). Facile release of carbon monoxide has been observed in manganese carbonyls containing acenaphthalene derivatives (Carrington et al., 2015) including the ligand MIAN {2-[(4-chlorophenyl)imino]acenapthylen-1-one}, the subject of this study, shown in the Scheme. Our crystal structure determination of MIAN at 90 K agrees with the structure reported by Kovach et al. (2011) at 100 K. In particular, the structure occurs in the triclinic space group P1 and it is found to be a twin. In the NMR study of MIAN by Kovach et al., major and minor species were detected in CDCl 3 at room temperature and a single species at 388 K in DMSO-d 6 . They suggested that an E to Z equilibration with the E form dominant takes place at the elevated temperature. The occurrence of a low-symmetry space group and twinning are indicative of a solid-solid phase change, and we were curious about the structure at higher temperatures. While a change of conformation from E to Z would be a very large solid-state change, an alternative structural change would be possible. At 250 K, a small solid-state change was indicated and the new space group is P2 1 /m ( phase). The only difference, aside from small differences in unit-cell dimensions, is a rotation of the iminoacenapthylen-1-one group into a crystallographic mirror plane. In each phase, the molecule remains in the E conformation. Structural commentaryThe crystal structure was initially determined at 90 K. Three twin domains were found, with relative contributions of 0.441 (2), 0.058 (3), 0.060 (3). Redetermination of the structure at higher temperatures validated our suspicion that the structure was temperature-sensitive. In order to more easily compare the low-temperature and room-temperature crystal structures, a non-standard setting for the triclinic form was selected. In this setting the shortest axis is the b axis. The b axis is then the unique axis in the monoclinic setting of P2 1 /...

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Section: Chemical Contextmentioning

confidence: 90%

A temperature-dependent phase transformation of (E)-2-[(4-chlorophenyl)imino]acenaphthylen-1-one

Bao

Olmstead

2017

Acta Cryst E

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“…All reagents were of commercial grade and were used without further purification unless stated otherwise. 2-(Pyridin-2-yl)-1,3-benzothiazole (pbt) (Chen et al, 2001) and 2-(quinolin-2yl)-1,3-benzothiazole (qbt) (Stenger-Smith et al, 2017) were synthesized following reported procedures. 1,10-Phenanthroline (phen) was purchased from Sigma-Aldrich Inc. and was used as received.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and structures of photoactive rhenium carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzothiazole, 2-(quinolin-2-yl)-1,3-benzothiazole and 1,10-phenanthroline

et al. 2017

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Carbon monoxide (CO) has recently been identified as a gaseous signaling molecule that exerts various salutary effects in mammalian pathophysiology. Photoactive metal carbonyl complexes (photoCORMs) are ideal exogenous candidates for more controllable and site-specific CO delivery compared to gaseous CO. Along this line, our group has been engaged for the past few years in developing group-7-based photoCORMs towards the efficient eradication of various malignant cells. Moreover, several such complexes can be tracked within cancerous cells by virtue of their luminescence. The inherent luminecscent nature of some photoCORMs and the change in emission wavelength upon CO release also provide a covenient means to track the entry of the prodrug and, in some cases, both the entry and CO release from the prodrug. In continuation of the research circumscribing the development of trackable photoCORMs and also to graft such molecules covalently to conventional delivery vehicles, we report herein the synthesis and structures of three rhenium carbonyl complexes, namely, fac-tricarbonyl[2-(pyridin-2-yl)-1,3-benzothiazole-κN,N'](4-vinylpyridine-κN)rhenium(I) trifluoromethanesulfonate, [Re(CHN)(CHNS)(CO)](CFSO), (1), fac-tricarbonyl[2-(quinolin-2-yl)-1,3-benzothiazole-κN,N'](4-vinylpyridine-κN)rhenium(I) trifluoromethanesulfonate, [Re(CHN)(CHNS)(CO)](CFSO), (2), and fac-tricarbonyl[1,10-phenanthroline-κN,N'](4-vinylpyridine-κN)rhenium(I) trifluoromethanesulfonate, [Re(CHN)(CHN)(CO)](CFSO), (3). In all three complexes, the Re center resides in a distorted octahedral coordination environment. These complexes exhibit CO release upon exposure to low-power UV light. The apparent CO release rates of the complexes have been measured to assess their comparative CO-donating capacity. The three complexes are highly luminescent and this in turn provides a convenient way to track the entry of the prodrug molecules within biological targets.

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“…This may be achieved by external stimuli such as enzymes, solvent, H 2 O 2 , , and light . The release of CO with the help of light is known as photoactivated CORMs (photo-CORMs), ,,− phot-CORMs has the advantage of controlled CO release. However, the general problem with most of the reported photo-CORMs is site specificity and predictable formation of a metal–coligand fragment, which might possess the biological activity of its own.…”

Section: Introductionmentioning

confidence: 99%

Vesicles Functionalized with a CO-Releasing Molecule for Light-Induced CO Delivery

Sakla

Jose

2018

ACS Appl. Mater. Interfaces

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In this paper, a new type of methodology to deliver carbon monoxide (CO) for biological applications has been introduced. An amphiphilic manganese carbonyl complex (1.Mn) incorporated into the 1,2-distearoyl-sn-glycero-3-phosphocholine lipid vesicles has been reported first time for the photoinduced release of CO. The liposomes (Ves-1.Mn) gradually released CO under light at 365 nm over a period of 50 min with a half-time of 26.5 min. The CO-releasing ability of vesicles appended with 1.Mn complexes has been confirmed by myoglobin assay and infrared study. The vesicles appended with 1.Mn have the advantages of biocompatibility, water solubility, and steady and slow CO release. This approach could be a rational approach for applying various water-insoluble photoinduced CO donors in aqueous media by using vesicles as a nanocarrier for CO release.

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Synthesis and structures of photoactive manganese–carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzothiazole and 2-(quinolin-2-yl)-1,3-benzothiazole

Cited by 5 publications

References 14 publications

A temperature-dependent phase transformation of (E)-2-[(4-chlorophenyl)imino]acenaphthylen-1-one

A temperature-dependent phase transformation of (E)-2-[(4-chlorophenyl)imino]acenaphthylen-1-one

Synthesis and structures of photoactive rhenium carbonyl complexes derived from 2-(pyridin-2-yl)-1,3-benzothiazole, 2-(quinolin-2-yl)-1,3-benzothiazole and 1,10-phenanthroline

Vesicles Functionalized with a CO-Releasing Molecule for Light-Induced CO Delivery

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