Novel oxorhenium complex of 4,5-diaza-fluoren-9-one-synthesis, spectroscopic characterization, X-Ray structure and DFT calculations

Machura, B.; Wolff, Mariusz; Świtlicka, A.

doi:10.1016/j.inoche.2010.09.017

Inorganic Chemistry Communications

2011

DOI: 10.1016/j.inoche.2010.09.017

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Novel oxorhenium complex of 4,5-diaza-fluoren-9-one-synthesis, spectroscopic characterization, X-Ray structure and DFT calculations

B. Machura

Mariusz Wolff

A. Świtlicka

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Cited by 3 publications

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“…In continuation of our interest in rhenium-based coordination compounds that might serve as radiopharmaceuticals, the title compound was synthesized. As imilar compound featuring bromido instead of chlorido ligands has recently been described in the literature [2]. The compound is acentrosymmetric dinuclear rhenium(V) coordination compound.…”

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confidence: 99%

Crystal structure of bis(4,5-diaza-fluoren-9-one-κ2N,N) dioxo-μ2- oxodirhenium(V)- acetonitrile (1:2), C26H18Cl4N6O5Re2

Mukiza

Gerber

Hosten

et al. 2014

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe compound was obtained upon reacting ReCl 3 (MeCN)(PPh 3 ) 2 with the chelating ligandinacetonitrile. Experimental detailsCarbon-boundHatoms were placed in calculated positions(C-H 0.95 Å) andwereincludedinthe refinement in the riding model approximation, with U iso (H) setto1.2U eq (C). The Hatoms of the methyl groups were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite[ 6]),w ith U iso (H)s et to 1.5U eq (C). DiscussionNext to cardiovascular diseases, cancer has become one of the main fatal diseases in industrializedcountries. Apart from classical surgery,chemo-and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from theirown setofproblematic side-effects and, as ac onsequence, the development of radiopharmaceuticals -combining the advantages of chemotherapyaswellasradiation methods while at the same timeavoiding theiruniquerespectiveundesired side-effects -has been atopic of research [1]. Tailoring andf ine-tuningo ft he envisioned radiopharmaceuticals'properties such as lipophilicity and, in particular, inertness is of paramount importance with respect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if amore heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In continuation of our interest in rhenium-based coordination compounds that might serve as radiopharmaceuticals, the title compound was synthesized. As imilar compound featuring bromido instead of chlorido ligands has recently been described in the literature [2]. The compound is acentrosymmetric dinuclear rhenium(V) coordination compound. The asymmetric unit contains half of the coordination compound as well as am olecule of acetonitrile. The latter is disordered over two positions at aratio of nearly 0.5:0.5. The two rhenium atomsa re connected by means of an oxido bridge.The central Re atoms are hexacoordinate. Therespective octahedral coordinationsphereiscompleted by means of achelating molecule of 4,5-diaza-fluoren-9-one as well as an oxido and two chlorido ligands in cis configuration. The two Re-O bond lengths of 1.699(3) Åand 1.9019(2) Åfor the double as well as the single bond, respectively, areingood agreement with values found for other compounds containing the O=Re-O-Re moiety whose structural data has been deposited with the Cambridge Structural Database [3].The twoRe-N bonds are nearlyidentical with respecttotheir length,afinding that also holdstruefor the twoRe-Cl bonds. TheRe-O-Re angleismeasured at 180°. The least-squares planes as defined by the non-hydrogen atomsofthe the two individual pyridine subunits present on the 4,5-diazafluoren-9-one ligand intersect at an angle of 0.6(3)°only.Inthe crystal, amultitude of C-H×××O, C-H×××Nand C...

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mentioning

confidence: 99%

Crystal structure of bis(4,5-diaza-fluoren-9-one-κ2N,N) dioxo-μ2- oxodirhenium(V)- acetonitrile (1:2), C26H18Cl4N6O5Re2

Mukiza

Gerber

Hosten

et al. 2014

Zeitschrift Für Kristallographie - New Crystal Structures

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Development of a highly selective cell-permeable ratiometric fluorescent chemosensor for oxorhenium(v) ion

Sen

Mukherjee

Sarkar

et al. 2011

Analyst

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A novel 6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c]quinazoline (HL) serves as a first-time highly selective and sensitive ratiometric fluorescent chemosensor probe for oxorhenium (ReO(V)) ion in acetonitrile : water = 9 : 1 (v/v) at 25 °C. The decrease in fluorescence at 410 nm and increase in fluorescence at 478 nm with an isoemissive point at 444 nm in the presence of ReO(V) ion is accounted for by the formation of mononuclear [ReOL(2)Cl] complex, characterized by physico-chemical and spectroscopic tools. The fluorescence quantum yield of the chemosensor (HL) was only 0.198 at 410 nm, and it increased more than 3-fold in the presence of 2 equiv. of the ReO(V) ion at 478 nm. Interestingly, the introduction of other metal ions and relevant anions caused the fluorescence intensity at 478 nm to be either unchanged or weakened. The fluorescence-response fits a Hill coefficient of 2.088 indicates the formation of a 1 : 2 stoichiometry for the L-ReO(V) complex. In the concentration range of 0-20 μM of oxorhenium(V) species calibration graph was linear with correlation coefficient (R) of 0.99994 and the calibration sensitivity was found to be 4.0 × 10(-7) M. The cellular image in the confocal microscope clearly indicated the presence of ReO(V) in Candida albicans cells using this chemosensor (HL).

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Coordination chemistry and applications of versatile 4,5-diazafluorene derivatives

Annibale

Song

2016

Dalton Trans.

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This perspective review will examine the coordination chemistry and applications of metal complexes of 4,5-diazafluorene derivatives. The versatile derivatives of 4,5-diazafluorene can serve multiple roles, and display a number of coordination modes. The ambidentate derivatives with multiple coordination sites can allow for the syntheses of coordination polymers, multimetallic, and macrocyclic complexes. In addition, certain 4,5-diazafluorene derivatives can serve as spectator ligands to support reactivity at the metal centre, or as reactive actor ligands engaging in atypical reactivity patterns. The applications of metal complexes of 4,5-diazafluorene derivatives in catalysis, photochemistry and photophysics, as well as in bioinorganic chemistry are also surveyed.

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Novel oxorhenium complex of 4,5-diaza-fluoren-9-one-synthesis, spectroscopic characterization, X-Ray structure and DFT calculations

Cited by 3 publications

References 48 publications

Crystal structure of bis(4,5-diaza-fluoren-9-one-κ2N,N) dioxo-μ2- oxodirhenium(V)- acetonitrile (1:2), C26H18Cl4N6O5Re2

Crystal structure of bis(4,5-diaza-fluoren-9-one-κ2N,N) dioxo-μ2- oxodirhenium(V)- acetonitrile (1:2), C26H18Cl4N6O5Re2

Development of a highly selective cell-permeable ratiometric fluorescent chemosensor for oxorhenium(v) ion

Coordination chemistry and applications of versatile 4,5-diazafluorene derivatives

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