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1.
Chemistry ; 2021 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-33851453

RESUMO

We present highly regioselective syntheses of 1,2-dicarboxylated cyclopentadienide salts [Cat] 2 [C 5 H 3 (CO 2 ) 2 H] by reaction of a variety of organic cation methylcarbonate salts [Cat]OCO 2 Me (Cat = NR 4 + , PR 4 + , Im + ) with cyclopentadiene (CpH) or by simply reacting organic cation cyclopentadienides Cat[Cp] (Cat = NR 4 + , PR 4 + , Im + ) with CO 2 . One characteristic feature of these dianionic ligands is the acidic proton delocalized in an intramolecular hydrogen bridge (IHB) between the two carboxyl groups, as studied by 1 H-NMR spectroscopy and XRD analyses. The reaction cannot be stopped after the first carboxylation. Therefore, we propose a Kolbe-Schmitt phenol-carboxylation related mechanism where the acidic proton of the monocarboxylic acid intermediate plays an ortho- directing and CO 2 activating role for the second kinetically accelerated CO 2 addition step exclusively in ortho position. The same and related thiocarboxylates [Cat] 2 [C 5 H 3 (COS) 2 H] are obtained by reaction of COS with Cat[Cp] (Cat = NR 4 + , PR 4 + , Im + ). A preliminary study on [Cat] 2 [C 5 H 3 (CO 2 ) 2 H] reveals, that its soft and hard coordination sites can selectively be addressed by soft Lewis acids (Mo 0 , Ru 2+ ) and hard Lewis acids (Al 3+ , La 3+ ).

2.
Artigo em Inglês | MEDLINE | ID: mdl-33724640

RESUMO

Herein we report a versatile concept for the synthesis of fourfold functionalized, soluble pyrenes, peropyrenes, terropyrenes and quarterropyrenes. They were obtained by a modular stepwise approach towards the rylene scaffold via Suzuki-Miyaura cross coupling, oxidative cyclodehydrogenation in the presence of caesium hydroxide under air and finally zinc mediated reductive silylation . The silylated reaction products were characterized by X-ray crystallography. The first example of a synthesized and crystallized quarterropyrene is presented and its oxidation reaction investigated. The functionalized rylenes were systematically characterized by means of UV-Vis-NIR and photoluminescence spectroscopy showing a bathochromic shift of 80 nm per naphthalene unit and a nearly linear increase of the extinction coefficients. Cyclic voltammograms and DFT calculations identify them as electron-rich dyes and show a narrowing of the electrochemically determined HOMO-LUMO gap and lower oxidation potentials for the higher homologues.

3.
Inorg Chem ; 59(23): 17565-17572, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-33197182

RESUMO

The syntheses and XRD molecular structures of a complete series of silylsulfido metalates Cat[M(SSiMe3)2] (M = Cu, Ag, Au) and corresponding silylselenido metalates Cat[M(SeSiMe3)2] (M = Cu, Ag, Au) comprising lattice stabilizing organic cations (Cat = Ph4P+ or PPN+) are reported. Much to our surprise these homoleptic cuprates, argentates, and aurates are stable enough to be isolated even in the absence of any strongly binding phosphines or N-heterocyclic carbenes as coligands. Their metal atoms are coordinated by two silylchalcogenido ligands in a linear fashion. The silyl moieties of all anions show an unexpected gauche conformation of the silyl substituents with respect to the central axis Si-[E-M-E]-Si in the solid state. The energetic preference for the gauche conformation is confirmed by quantum chemical calculations and amounts to about 2-6 kJ/mol, thus revealing a rather shallow potential mainly depending on electronic effects of the metal. Furthermore, 2D HMQC methods were applied to detect the otherwise nonobservable NMR shifts of the 29Si and 77Se nuclei of the silylselenido compounds. Preliminary investigations reveal that these thermally and protolytically labile chalcogenido metalates are valuable precursors for the precipitation of binary coinage metal chalcogenide nanoparticles from organic solution and for coinage metal cluster syntheses.

4.
ACS Nano ; 14(11): 15766-15775, 2020 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-33186031

RESUMO

We revisit the question of kekulene's aromaticity by focusing on the electronic structure of its frontier orbitals as determined by angle-resolved photoemission spectroscopy. To this end, we have developed a specially designed precursor, 1,4,7(2,7)-triphenanthrenacyclononaphane-2,5,8-triene, which allows us to prepare sufficient quantities of kekulene of high purity directly on a Cu(111) surface, as confirmed by scanning tunneling microscopy. Supported by density functional calculations, we determine the orbital structure of kekulene's highest occupied molecular orbital by photoemission tomography. In agreement with a recent aromaticity assessment of kekulene based solely on C-C bond lengths, we conclude that the π-conjugation of kekulene is better described by the Clar model rather than a superaromatic model. Thus, by exploiting the capabilities of photoemission tomography, we shed light on the question which consequences aromaticity holds for the frontier electronic structure of a π-conjugated molecule.

5.
Molecules ; 25(17)2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32883039

RESUMO

A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu-Cu distances in the range 2.55-2.67 Å. In order to enhance conformational rigidity within the characteristic Cu-C-Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2-9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14-18. Neutral complexes were typically obtained via the reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1'-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared, and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (ΦPL) were determined to be 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

6.
Dalton Trans ; 49(35): 12180-12183, 2020 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-32930682

RESUMO

A single thiocatecholate group has been combined with a phthalocyanine and used to coordinate a [Ni(dppe)]2+ fragment to give the unprecedented title complex [(dppe)Ni(S2PcH2)]. UV-Vis spectroscopy shows new strong transitions in the Q-band, which TDDFT calcualtions predict result from internal charge transfer processes. Insights are gained with respect to designing future photocatalytic systems.

7.
Inorg Chem ; 59(17): 12054-12064, 2020 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-32822178

RESUMO

Previous reports in the literature describe that the crystallization of hexaphenyl carbodiphosphorane (CDPPh) from a variety of solvents gives a "bent" geometry for the P-C-P moiety as the solid-state molecular structure. However, a linear structure is observed when CDPPh is crystallized from benzene. Here, we report detailed spectroscopic and theoretical studies on the linear and bent structures. X-ray powder diffraction examinations show a phase transition of linear CDPPh upon the loss of co-crystallized benzene molecules, which is accompanied by the bending of the P-C-P unit. Studies on the linear and bent structures (i.e., X-ray powder diffraction, solid-state NMR, UV-vis spectroscopy, and IR spectroscopy) show significant differences in their properties. Investigations of the solid-state structures with density functional theory-based methods (PBE-D3) point toward subtle dispersion effects being responsible for this solvent-induced bond-bending isomerism in CDPPh.

8.
Dalton Trans ; 49(8): 2517-2526, 2020 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-32022066

RESUMO

Organic cation salts with homoleptic zincate and stannanide anions, Ph4P [Zn(ESiMe3)3] (E = S (1a), Se (1b)) and Cat [Sn(ESiMe3)3] (Cat = Ph4P+ (E = S (2a-Ph4P); Cat = PPN+ (E = S 2a-Ph4P, Se (2a)) are presented and structurally characterized. Efforts to isolate neutral thermally metastable stannane precursors [Sn(ESiMe3)4] (E = S (3), Se(4)) are reported as well. The thermal decomposition of the presented precursors to yield binary sulfides and selenides of zinc and tin is investigated. Furthermore, the potential of using the title anions as precursors in solution-based low-temperature synthesis of Cu2ZnSnS4 (CZTS) by coprecipitation with [Cu(tmtu)3]PF6 and subsequent annealing is discussed.

9.
Inorg Chem ; 59(6): 3428-3436, 2020 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-31967797

RESUMO

Phase-pure crystalline Bi2Se3 and Bi2Te3 nanoparticles are formed in reactions of [C4C1Im]3[Bi3I12] (C4C1Im = 1-butyl-3-methylimidazolium) with [C4C1Pyr][ESiMe3] (E = Se or Te; C4C1Pyr = 1-butyl-1-methylpyrrolidinium) in the ionic liquid (IL) [C4C1Im]I. The resulting crystalline tetradymite-type nanoparticles exhibit stoichiometric Bi:E (E = Se or Te) molar ratios (2:3). Because all synthetic steps were performed under strict inert gas conditions, the surfaces of the Bi2Se3 and Bi2Te3 nanoparticles are free of metal oxide species. As proven by infrared and X-ray photoelectron spectroscopy analyses, the nanoparticle surfaces reveal only minor organic contamination from solvent residues ([C4C1Im]I). The nanomaterials show high Seebeck coefficients of -124 µV K-1 (Bi2Se3) and -155 µV K-1 (Bi2Te3) and feature high electrical conductivities (328 and 946 S cm-1, respectively) at the highest tested temperature (240 °C). The corresponding thermal conductivities (0.8 and 2.3 W m-1 K-1, respectively, at 30 °C) are comparable to those of single crystals and recently reported ab initio calculations, which is in remarkable contrast to typical findings of nanograined bulk materials obtained from compacted nanoparticles. These findings emphasize the low level of impurities, surface contamination, and, in general, defects produced by the synthetic approach reported here. The figure of merit in the in-plane direction of the compacted pellets reached peak values 0.45 for Bi2Se3 and 0.4 for Bi2Te3.

10.
J Am Chem Soc ; 142(2): 894-899, 2020 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-31840996

RESUMO

The synthesis of cycloarenes in solution is challenging because of their low solubility and the often hindered cyclodehydrogenation reaction of their nonplanar precursors. Using an alternative on-surface synthesis protocol, we achieved an unprecedented double-stranded hexagonal cycloarene containing 108 sp2 carbon atoms. Its synthesis is based on hierarchical Ullmann coupling and cyclodehydrogenation of a specially designed precursor on a Au(111) surface. The structure and other properties of the cycloarene are investigated by scanning tunneling microscopy/spectroscopy, atomic force microscopy, and density functional theory calculations.

11.
Inorg Chem ; 58(22): 15385-15392, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31687815

RESUMO

We communicate the synthesis and full characterization of so far unknown tetrakis(trimethylsilylsulfido) and -(trimethylsilylselenido) gallates and indates in form of their organic salts Cat+[M(ESiMe3)4]- (M = Ga, In; E = S, Se; Cat = dimethylpyrrolidinium (DMPyr+), Ph4P+, (dppe)2Cu+, (dmpe)2Cu+). These thermally metastable silylchalcogenolatometalates can act as modular precursors for an ionic-liquid- or organic-solution-based low-temperature synthesis of multinary metal chalcogenide materials such as the CIGS species Cu(InxGa1-x)(SySe1-y)2.

12.
Nat Commun ; 10(1): 5049, 2019 11 06.
Artigo em Inglês | MEDLINE | ID: mdl-31695045

RESUMO

Phthalocyanines possess unique optical and electronic properties and thus are widely used in (opto)electronic devices, coatings, photodynamic therapy, etc. Extension of their π-electron systems could produce molecular materials with red-shifted absorption for a broader range of applications. However, access to expanded phthalocyanine analogues with more than four isoindoline units is challenging due to the limited synthetic possibilities. Here, we report the controlled on-surface synthesis of a gadolinium-supernaphthalocyanine macrocycle and its open-chain counterpart poly(benzodiiminoisoindoline) on a silver surface from a naphthalene dicarbonitrile precursor. Their formation is controlled by the on-surface high-dilution principle and steered by different metal templates, i.e., gadolinium atoms and the bare silver surface, which also act as oligomerization catalysts. By using scanning tunneling microscopy, photoemission spectroscopy, and density functional theory calculations, the chemical structures along with the mechanical and electronic properties of these phthalocyanine analogues with extended π-conjugation are investigated in detail.

13.
Org Lett ; 21(22): 9142-9146, 2019 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-31680528

RESUMO

With the synthesis of N,N',N″,N‴-tetrakis(3-(dimethylamino)propyl)triaminophosphazene (TDMPP, 1), we present the first phosphazene superbase with enhanced basicity through the effect of multiple intramolecular hydrogen bonding (IHB). Due to intramolecular solvation of four NH protons, the proton affinity is even higher than that of second-order phosphazene (dma)P2-tBu. X-ray structural proof, NMR titration experiments, and computational investigations provide a more detailed quantitative description of the IHB influence on the superbasicity of 1 in solid-state, solution, and the gas-phase.

14.
Dalton Trans ; 48(29): 10971-10978, 2019 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-31210231

RESUMO

We present convenient syntheses of so far inaccessible, crystalline and highly pure 1,3-dialkylimidazolium salts with extremely nucleophilic thiolate and selenolate anions [ER]- (R = H, tBu, SiMe3). While non existent for E = O, the title compounds exist as slightly less basic E = S and Se homologues. The anion cation H-bond interactions in the crystalline state have been studied systematically in six related ionic compounds of varying anion basicity and steric bulk, namely MMIm [SH] (1), MMIm [StBu] (2), and MMIm [SSiMe3] (3), as well as MMIm [SeH] (4), MMIm [SetBu] (5) and MMIm [SeSiMe3] (6). The chalcogenolate title compounds 3, 5, and 6 are prepared by the newly introduced method of desilylation of Me3Si-ER (E = S, Se) by the super-nucleophile MMIm [StBu] (2), which is easily accessible via deprotonation of HStBu with in situ generated NHC 1,3-dimethylimidazolidin-2-ylidene. Focus is put on the role of the most acidic imidazolium proton C2-H as structural director and as 1H NMR shift indicator. These salts show an unusually high volatility and tendency to sublime under vacuum without irreversible decay.

15.
Angew Chem Int Ed Engl ; 58(30): 10335-10339, 2019 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-31037821

RESUMO

It was discovered that phosphazenyl phosphines (PAPs) can be stronger P-superbases than the corresponding Schwesinger type phosphazene N-superbases. A simple synthetic access to this class of PR3 derivatives including their homologization is described. XRD structures, proton affinities (PA), and gas-phase basicities (GB) as well as calculated and experimental pK BH + values in THF are presented. In contrast to their N-basic counterparts, PAPs are also privileged ligands in transition metal chemistry. In fact, they are currently the strongest uncharged P-donors known, exceeding classical and more recently discovered ligands such as PtBu3 and imidazolin-2-ylidenaminophosphines (IAPs) with respect to their low Tolman electronic parameters (TEPs) and large cone angles.

16.
Chem Sci ; 10(41): 9483-9492, 2019 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-32055322

RESUMO

A new generation of carbodiphosphoranes (CDPs), incorporating pyrrolidine, tetramethylguanidine, or tris(dimethylamino)phosphazene as substituents is introduced as the most powerful class of non-ionic carbon superbases on the basicity scale to date. The synthetic approach as well as NMR spectroscopic and structural characteristics in the free and protonated form are described. Investigation of basicity in solution and in the gas phase by experimental and theoretical means provides the to our knowledge first reported pK BH + values for CDPs in the literature and suggest them as upper tier superbases.

17.
Dalton Trans ; 47(45): 16255-16263, 2018 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-30398259

RESUMO

A new and facile method of generating thiolate groups at the phthalocyanine (Pc) ß-position is presented as well the unique properties that these groups confer on the Pc ligand upon coordination of group 10 metals Ni, Pd and Pt(dppe) or SnMe3. In particular, the Q-band is shifted to almost 800 nm for all group 10 metals used, and the complexes show panchromatic absorption owing to new absorbance bands that appear between 400 and 650 nm. Enhanced intersystem-crossing for all transition metal coordinated Mg(Pc) complexes was demonstrated by the moderate to very high singlet oxygen quantum yields of 0.36, 0.76 and 0.91 for the Ni, Pd and Pt coordinating complexes, respectively, which show that the heavy metals have direct influence on the Pc π-system and inter-system-crossing (ISC). This was further confirmed by MO calculations, which show mixing of metal and ligand orbitals, as well as suggest that the Q-band transition has both π → π* and ligand-to-metal charge transfer characteristics. Furthermore, the origin of the Q-band red-shift was shown to be due to greater destabilization of the HOMO compared to LUMO/LUMO+1, thus decreasing the HOMO-LUMO band gap.

18.
Dalton Trans ; 47(47): 17067-17076, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30465052

RESUMO

In a previous investigation, it was shown that [Cu(tpym)(PPh3)]PF61 with tpym = tris(2-pyridyl)methane represents a deep blue emitter (λmax = 466 nm) though with a low emission quantum yield ΦPL if doped in a polymer (7%) or dissolved in a fluid solvent (≪1%). In this study, we present new tripod compounds with sterically demanding ligands: [Cu(tpym)(P(o-tol)3)]PF62 and [Cu(tpym)(P(o-butyl-ph)3)]PF63 with P(o-tol)3 = tris(ortho-tolyl)phosphine and P(o-butyl-ph)3 = tris(ortho-n-butylphenyl)phosphine. These compounds show high emission quantum yields even in a fluid solution (dichloromethane) reaching a benchmark value for 3 of ΦPL = 76%. This becomes possible due to the specific design of rigidifying the complexes. Importantly, the deep blue emission color is maintained or even further blue shifted to λmax = 452 nm (compound 3 powder). Compound 2 is characterized photophysically in detail. In particular, it is shown that the lowest excited triplet state T1 experiences very efficient spin-orbit coupling (SOC). Accordingly, the phosphorescence decay rate is as large as 5 × 104 s-1 (20 µs) belonging to the fastest T1→ S0 transition values (shortest decay times) reported so far. Investigations down to T = 1.5 K reveal a large total zero-field splitting (ZFS) of 7 cm-1 (0.9 meV). Although thermally activated delayed fluorescence (TADF) grows in at T≥ 160 K, the phosphorescence of 2 still dominates (60%) over TADF (40%) at ambient temperature. Thus, the compound represents a singlet harvesting-plus-triplet harvesting material, if applied in an OLED.

19.
Org Biomol Chem ; 16(35): 6586-6599, 2018 09 11.
Artigo em Inglês | MEDLINE | ID: mdl-30168830

RESUMO

Herein, we present a series of isomerically pure, peripherally alkyl substituted, soluble and low aggregating azaphthalocyanines as well as their new, smaller hybrid homologues, azasubphthalocyanines. The focus lies on the effect of the systematically increasing number of aza building blocks [-N[double bond, length as m-dash]] replacing the non-peripheral [-CH[double bond, length as m-dash]] units and their influence on the physical and photophysical properties of these chromophores. The absolute and relative HOMO-LUMO energies of azaphthalocyanines were analyzed using UV-Vis and CV and compared to the density functional theory calculations (B3LYP, TD-DFT). The lowering of the HOMO level is revealed as the determining factor for the trend in the adsorption energies by electronic structure analysis. Crystals of substituted subphthalocyanines, N2-Pc*H2 and N4-[Pc*Zn·H2O], were obtained out of DCM. For the synthesis of the valuable tetramethyltetralin phthalocyanine building block a new highly efficient synthesis involving a nearly quantitative CoII catalyzed aerobic autoxidation step is introduced replacing inefficient KMnO4/pyridine as the oxidant.

20.
Dalton Trans ; 47(6): 1933-1941, 2018 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-29340393

RESUMO

New ferrocenylsulfonium cation based ionic liquids were prepared by direct alkylation of the corresponding ferrocenyl-based thioethers with N-alkylbis(trifluoromethanesulfonyl)imides (R'TFSI). This convenient direct access to organometallic sulfonium bis(trifluoromethanesulfonyl)imide (TFSI) salts without the need for ion exchange was chosen in order to obtain highly pure and reversibly redox active room temperature ILs in many cases. In other cases the anion cation interaction in the solid state was studied by XRD analyses. Moreover a diferrocenylmethylsulfonium tetrafluoroborate with two redox active centers was synthesized. The redox chemistry of these sulfonium salts was investigated via cyclic voltammetry. Furthermore, UV-Vis spectra and thermoanalytical data are discussed. The electron-withdrawing sulfonium group is directly bonded to the ferrocenyl unit, therefore this cationic group influences the potential of these ionic liquids in a more pronounced way than being anchored to the ferrocenyl unit via an organic spacer. With their low absorbance in the visible light and reversible, tunable redox potential, these room temperature ILs open perspectives as redox mediators in dye sensitized solar cells (DSSCs), as redox electrolytes in supercapacitors or as overcharge protection additives in batteries.

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