0000000000065981
AUTHOR
Ivana Císařová
Tuning the photophysical properties of anti-B18H22: efficient intersystem crossing between excited singlet and triplet states in new 4,4'-(HS)2-anti-B18H20.
The tuning of the photophysical properties of the highly fluorescent boron hydride cluster anti-B18H22 (1), by straightforward chemical substitution to produce 4,4'-(HS)2-anti-B18H20 (2), facilitates intersystem crossing from excited singlet states to a triplet manifold. This subsequently enhances O2((1)Δg) singlet oxygen production from a quantum yield of ΦΔ ∼ 0.008 in 1 to 0.59 in 2. This paper describes the synthesis and full structural characterization of the new compound 4,4'-(HS)2-anti-B18H20 (2) and uses UV-vis spectroscopy coupled with density functional theory (DFT) and ab initio computational studies to delineate and explain its photophysical properties.
Substitution of the laser borane anti-B18H22 with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides
Reaction of anti-B18H221 with pyridine in neutral solvents gives sparingly soluble B16H18-3',8'-Py23a as the major product (ca. 53%) and B18H20-6',9'-Py22 (ca. 15%) as the minor product, with small quantities of B18H20-8'-Py 4 (ca. 1%) also being formed. The three new compounds 2, 3a and 4 are characterized by single-crystal X-ray diffraction analyses and by multinuclear multiple-resonance NMR spectroscopy. Compound 2 is of ten-vertex nido:ten-vertex arachno two-atoms-in-common architecture, long postulated for a species with borons-only cluster constitution, but previously elusive. Compound 3a is of unprecedented ten-vertex nido:eight-vertex arachno two-atoms-in-common architecture. The si…
Amino‐Substituted Ferra‐bis(tricarbollides) − Metallatricarbaboranes Designed for Linear Molecular Constructions
Reactions between high purity FeCl2 and the anion [nido-7-(tBuHN)-7,8,9-C3B8H10)]− (1−) have been used for efficient syntheses of the twelve-vertex double-cluster metallatricarbollide complexes of the para,para (p,p) type [closo-9,9′(RHN)2-commo-2,2′-FeII-1,7,9-(C3B8H10)-1′,7′,9′-(C3B8H10)] (2) (2a, R = tBu and 2b, R = H) (yields 42−45% for 2a). Compound 2b, which contains two reactive amino substituents conveniently attached to the tricarbollide subclusters in p-positions with respect to the metal center, was prepared via facile cleavage of the tBu substituent in 2a either by AlCl3 or by thermal means. The structure of 2b constitutes a good setting for the synthesis of building blocks for …
Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone
International audience; Anionic phosphinoferrocene amidosulfonates bearing sterically demanding t-butyl substituents in positions 3 and 3' of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η5-tBuC5H3PR2)(η5-tBuC5H3C(O)NHCH2SO3)] (R = phenyl and cyclohexyl) were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η5-tBuC5H3PR2)(η5-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-t-butylated analogues have been used as lig-ands to prepare zwitterionic (η3-allyl)palladium(II) complexes [Pd(η3-C3H5){Fe(η5-R'C5H3PR2)(η5-R'C5H3C(O)NHCH2SO3)}] (R' = H, tBu, R = Ph, Cy). Depending on the isolation procedure and crystallization condi-tions, some complexes we…
Cobalt bis(dicarbollides)(1-) covalently attached to the calyx[4]arene platform: the first combination of organic bowl-shaped matrices and inorganic metallaborane cluster anions
Various calix[4]arene and resorc[4]arene ionic compounds substituted by cobalt bis(dicarbollide) anions (1) have been prepared for the first time. From tBu-calix[4]arene (A) the complete series of mono-, di-, tri- and tetrasubstituted derivatives bearing one to four cluster anions on the lower rim (3-6) have been obtained in the form of their alkali-metal salts by O-alkylation with the 1-dioxane derivative [8-O(CH2CH2)2O(+)-1,2-C2B9H10)-(1',2'-C2B9H11)-3,3'-Co] (2), all of which are syn or cone isomers. In contrast, disubstitution of the dipropyl ether of tBu-calix[4]arene (B) led to a mixture of the cone and 1,3-alternate conformers 7a and 7b, respectively. Starting from tetrapropoxy-calix…
Reactions of titanocene-bis(trimethylsilyl)ethyne complexes with diethynylsilane derivatives
Titanocene complexes [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 4 and 5) react uniformly with siladiynes R 2 2 Si(CCR 1 ) 2 , where R 1 =Ph, and R 2 =Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η 5 -cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η 5 -C 5 H 5− n Me n ) 2 Ti{R 1 2 C 4 (SiR 2 2 )}]. Products arising from [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 2 (1,3-isomer), 4 and 5) and Me 2 Si(CCCMe 3 ) 2 vary with n : the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated t…
The Zwitterion [8,8′-μ-CH2O(CH3)-(1,2-C2B9H10)2-3,3′-Co]0 as a Versatile Building Block To Introduce Cobalt Bis(Dicarbollide) Ion into Organic Molecules
The synthesis of a new bridged [8,8′-μ-CH2O(CH3)-(1,2-C2B9H10)2-3,3′-Co]0 derivative (2), arising from the acid-catalyzed reaction of cobalt bis(1,2-dicarbollide)(1−) ion with formaldehyde, is reported. The proposed reaction path is supported by the isolation of side products including two zwitterionic compounds, the known bridged [8,8′-μ-(CH3O)-(1,2-C2B9H10)2-3,3′-Co]0 derivative (3), the new zwitterion [(8-(CH3)2O-1,2-C2B9H10)-(1′,2′-C2B9H11)-3,3′-Co]0 (4), and two anionic compounds—the known [(8,8′-Cl2-1,2-C2B9H10)2-3,3′-Co]− and the newly characterized dimethoxy derivative [(8,8′-(CH3O)2-1,2-C2B9H10)2-3,3′-Co]− of the cobalt bis(dicarbollide) ion. Compound 2 serves as a versatile buildi…
Structure, properties and comparison of C,N-chelated and amido-stabilized plumbylenes
The molecular structure of {2-[(CH3)2NCH2]C6H4}2Pb (1) in the solid state was determined by X-ray diffraction techniques on a single crystalline material. Bulky amido ligand stabilized complexes [(i-C3H7)2C6H3]NHLi (2) and [(i-C3H7)2C6H3N(Me3Si)]2Pb (3) were synthesized and characterized both in the solid state and solution by 1H, 13C, 15N and 207Pb NMR and XRD techniques. The structure of both C,N-chelated and bulky amido plumbylenes is compared.
Ir-Catalyzed Cycloaddition of Tribenzocyclyne with Biphenylenes
We demonstrate that Ir-catalyzed C-C bond activation in biphenylenes followed by a reaction with tribenzocyclyne is a suitable method for synthesizing strained and unknown monoadducts with the tetradehydrotetrabenzo[a,c,e,i]cyclododecene scaffold ([12]annulenes). Modification of reaction conditions also furnished [12]annulene products with cis and/or trans double bonds formed by hydrogen transfer. The [9]annulene side product was formed upon the reaction of the benzyl radical with tribenzocyclyne during the Bergman cyclization. All isolated compounds were fully characterized by HRMS, NMR, and X-ray diffraction analysis.
Titanium and zirconium complexes containing the new 2,3-dimethyl-1,4-diphenylcyclopentadienyl ligand. Synthesis, characterization and polymerization behavior
Abstract An easy and inexpensive three-step synthesis of new 2,3-dimethyl-1,4-diphenylcyclopentadiene (3) ligand and the titanium and zirconium homometallocene dichlorides [TiCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (4), [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (5), and the mixed ligand zirconium complex [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)(η5-C5H5)] (6) prepared thereof are described. The polymerization of ethene using 4–6/MAO catalysts revealed that zirconocene complexes 5 and 6 displayed moderate and high activity, respectively, whereas the titanium catalyst 4/MAO was inactive. The crystal structures of 4 and 5 were determined by X-ray crystallography.
Effect of Iodination on the Photophysics of the Laser Borane anti-B18H22: Generation of Efficient Photosensitizers of Oxygen
Treatment of the laser borane anti-B18H22 (compound 1) with iodine in ethanol gives the monoiodinated derivative 7-I-anti-B18H21 (compound 2) in 67% yield, or, by reaction with iodine or ICl in the presence of AlCl3 in dichloromethane, the diiodinated derivative 4,4'-I2-anti-B18H20 (compound 3) in 85% yield. On excitation with 360 nm light, both compounds 2 and 3 give strong green phosphorescent emissions (λmax = 525 nm, ΦL = 0.41 and λmax = 545 nm, ΦL = 0.71 respectively) that are quenched by dioxygen to produce O2(1Δg) singlet oxygen with quantum yields of ΦΔ = 0.52 and 0.36 respectively. Similarly strong emissions can be stimulated via the nonlinear process of two-photon absorption when …
Highly Functionalized Brønsted Acidic/Lewis Basic Hybrid Ferrocene Ligands: Synthesis and Coordination Chemistry
International audience; A general challenging issue in the synthesis of hemilabile ferrocene ligands is the access to highly functionalized ferrocene starting materials. These can bear donor/acceptor atoms, additional functional and structuring spectator substituents, but the preparation of such species poses general synthetic difficulties. We report herein alternative synthetic routes to hybrid ferrocene donors such as tert-butylated phosphanylcarboxylic acids and their corresponding aldehydes. These hybrid ambiphilic species that combine Brønsted-acidic and Lewis-basic functional moieties in their structure were characterized by multinuclear NMR and single-crystal X-ray diffraction analys…
CCDC 1441506: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Tomáš Jelínek, John D. Kennedy, Ivana Císařová, Robert D. Kennedy, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Kamil Lang, William Clegg|2018|Dalton Trans.|47|1709|doi:10.1039/C7DT03823B
CCDC 1877098: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877102: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877097: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877101: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877094: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1859436: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Jonathan Bould, Jakub Braborec, Kaplan Kirakci, Kamil Lang, Ivana Císařová, Pavel Kubát, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Lenka Slušná, Eva Noskovičová, Dušan Lorenc|2019|Inorg.Chem.|58|10248|doi:10.1021/acs.inorgchem.9b01358
CCDC 1441507: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Tomáš Jelínek, John D. Kennedy, Ivana Císařová, Robert D. Kennedy, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Kamil Lang, William Clegg|2018|Dalton Trans.|47|1709|doi:10.1039/C7DT03823B
CCDC 1877100: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1441504: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Tomáš Jelínek, John D. Kennedy, Ivana Císařová, Robert D. Kennedy, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Kamil Lang, William Clegg|2018|Dalton Trans.|47|1709|doi:10.1039/C7DT03823B
CCDC 1859437: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Jonathan Bould, Jakub Braborec, Kaplan Kirakci, Kamil Lang, Ivana Císařová, Pavel Kubát, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Lenka Slušná, Eva Noskovičová, Dušan Lorenc|2019|Inorg.Chem.|58|10248|doi:10.1021/acs.inorgchem.9b01358
CCDC 1877096: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1877099: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 1441505: Experimental Crystal Structure Determination
Related Article: Michael G. S. Londesborough, Jiří Dolanský, Tomáš Jelínek, John D. Kennedy, Ivana Císařová, Robert D. Kennedy, Daniel Roca-Sanjuán, Antonio Francés-Monerris, Kamil Lang, William Clegg|2018|Dalton Trans.|47|1709|doi:10.1039/C7DT03823B
CCDC 1877095: Experimental Crystal Structure Determination
Related Article: Léa Radal, Petr Vosáhlo, Julien Roger, Hélène Cattey, Régine Amardeil, Ivana Císařová, Petr Štěpnička, Nadine Pirio, Jean‐Cyrille Hierso|2019|Eur.J.Inorg.Chem.||865|doi:10.1002/ejic.201801378
CCDC 912917: Experimental Crystal Structure Determination
Related Article: Vicenta Saurí, Josep M. Oliva, Drahomír Hnyk, Jonathan Bould, Jakub Braborec, Manuela Merchán, Pavel Kubát, Ivana Císařová, Kamil Lang, and Michael G. S. Londesborough|2013|Inorg.Chem.|52|9266|doi:10.1021/ic4004559