RESUMO
Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electron lone pairs of electronegative atoms. This study examines the impact of remote substituents on select families of HVI compounds as means to achieve predictable two-dimensional extended solid-state materials. Crystallographic analyses of 10 HVI compounds from several related classes of λ3 organoiodine(III) compounds, (diacetoxyiodo)benzenes, (dibenzoatoiodo)benzenes, [bis(trifluoroacetoxy)iodo]benzenes, and µ-oxo-[(carboxylateiodo)benzenes], provide insights into how remote substituents and the choice of carboxylate groups can impact intermolecular interactions in the solid state.
RESUMO
Fluorescent molecules and materials that exhibit emission changes in response to analytes are of great interest across multiple disciplines. Herein, we investigate the response of NH-containing fluorophores carbazole and 2-phenylbenzimidazole (Ph-BIM) with two representative isolable singlet carbenes. Specifically, N-heterocyclic carbene 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and cyclic (alkyl)(amino)carbene (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene (EtCAAC) were discovered to afford three different types of reaction products with carbazole and Ph-BIM. Depending on the reaction pair, hydrogen bonding (1), NH-insertion (2,3), or proton transfer (4) products can be isolated, each displaying variable photophysical responses. These products have been structurally authenticated by single crystal X-ray diffraction and NMR spectrometric methods. Studies of the solution state behavior of 1-4 reveals that these adducts are labile and can reversibly dissociate to free carbenes and fluorophores to varying extents. These equilibria produce concentration dependent solution state behavior as identified and quantified via UV-visible absorption, emission, 1H DOSY, and NMR spectroscopic measurements.
RESUMO
This chapter overviews the roles of transition metal complexes having the organoiodine(III) reagents iodosylarenes (ArIO) and (imino)iodoarenes (ArINR) as ligands in catalysis. Mechanistic implications are discussed.
RESUMO
The functionalized catecholate, tetraethyl (2,3-dihydroxy-1,4-phenylene)bis(phosphonate) (H2 -DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)2], Li[B(DPC)F2], and Li[P(DPC)3]. The phosphoryl-rich character of these anions was designed to impart flame-retardant properties for their use as potential flame-retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium-ion batteries. The new materials were fully characterized, and the single-crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)3] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion.
RESUMO
A series of nine 1,4-distyrylfluorene derivatives (2) functionalized with substituents of variable electrondonating or -accepting capabilities was synthesised. The photophysical properties of the molecules were investigated, including UV/vis absorption, photoluminescence emission, and fluorescence quantum yields. Photophysical properties of chromophores 2 were found to exhibit significant solvatochromic effects, especially in the Stokes shift and photoluminescence maxima. The electrochemical properties of series 2 were also assessed by cyclic voltammetry and differential pulse voltammetry. Results of photophysical and electrochemical analyses were further supported by DFT calculations (B3LYP/6-31G*) and single crystal X-ray diffraction on select molecules. The contributions of intermolecular π-stacking and hydrogen bonding to crystal packing are discussed. A series of nine 1,4-distyrylphenylene derivatives (3) were also synthesised and similarly characterized for comparison to photophysical and solvatochromic effects observed in series 2. Properties of similarly-substituted molecules in series 2 and 3 were compared to one another in order to assess the influence of the 1,4-fluorenylene unit.
RESUMO
A bulky 1,4-di-iodobenzene having four adjacent para-tBu-C6H4 group (Ar') substituents (1) was used to prepare the di-hypervalent iodine compound 1,4-[I(OAc)2]2-2,3,5,6-Ar'4-C6 (2). Despite the steric encumbrance of the iodine center by the flanking aryl substituents, compound 2 undergoes ready cyclization under mild conditions (excess CF3COOH at 55 °C, 30 min) to afford a dicyclic di-iodonium di-triflate salt 3. The single crystal structures of compounds 2 and 3 were examined and compared to the formerly characterized precursor 1. The para-tert-butyl groups on these compounds also render the compounds more soluble than multifunctional hypervalent iodine (HVI) compounds. HVI compounds having multiple iodine(III) centers are increasingly of interest for applications as recyclable reagents, materials precursors, and as Lewis acids.
RESUMO
2-R-1H-1,3-Benzazaphospholes (R-BAPs) are an interesting class of σ2P heterocycles containing P[double bond, length as m-dash]C bonds. While closely related 2-R-1,3-benzoxaphospholes (R-BOPs) have been shown to be highly photoluminescent materials depending on specific R substituents, photoluminescence of R-BAPs has been previously limited to an example having a fused carbazole ring system. Here we detail the synthesis and structural characterization of a new R-BAP (3c, R = 2,2'-dithiophene), and compare its photoluminescence against two previously reported R-BAPs (3a, R, R' = Me and 3b, R = 2-thiophene). The significant fluorescence displayed by the thiophene derivatives 3b (φ = 0.53) and 3c (φ = 0.12) stands in contrast to the weakly emissive methyl substituted analogue 3a (φ = 0.08). Comparative computational investigations of 3a-c offer insights into the interplay between structure-function relationships affecting excited state relaxation processes.
RESUMO
Single crystal structures have been determined for the three cofacial, oxygen-bridged, silicon phthalocyanine oligomers, [((CH(3))(3)SiO)(2)(CH(3))SiO](SiPcO)(2-4)[Si(CH(3))(OSi(CH(3))(3))(2)], and for the corresponding monomer. The data for the oligomers give structural parameters for a matching set of three cofacial, oxygen-bridged silicon phthalocyanine oligomers for the first time. The staggering angles between the six adjacent cofacial ring pairs in the three oligomers are not in a random distribution nor in a cluster at the intuitively expected angle of 45° but rather are in two clusters, one at an angle of 15° and the other at an angle of 41°. These two clusters lead to the conclusion that long, directional interactions (LDI) exist between the adjacent ring pairs. An understanding of these interactions is provided by atoms-in-molecules (AIM) and reduced-density-gradient (RDG) studies. A survey of the staggering angles in other single-atom-bridged, cofacial phthalocyanine oligomers provides further evidence for the existence of LDI between cofacial phthalocyanine ring pairs in single-atom-bridged phthalocyanine oligomers.
Assuntos
Indóis/química , Compostos de Organossilício/química , Cristalografia por Raios X , Modelos Moleculares , Estrutura Molecular , Teoria Quântica , EstereoisomerismoRESUMO
Several new bifunctional salts, Li[B(DPN)2], Li[B(DPN)(ox)] and Li[P(DPN)3], have been prepared from the phosphorus(v)-containing chelating ligand 2,3-dihydroxynaphthalene-1,4-(tetraethyl)bis(phosphonate) (H2-DPN). The new lithium salts were characterized by a variety of spectroscopic techniques. Both H2-DPN and Li[B(DPN)2] have been structurally characterized by X-ray crystallographic methods. These salts are related to materials being examined for use in electrolyte solutions for lithium-ion battery (LIB) applications.
RESUMO
The syntheses of benzoxaphospholes and new benzobisoxaphospholes that display blue fluorescence are presented. The latter compounds were accessed by the use of a new precursor, 2,5-diphosphinohydroquinone. The new compounds were fully characterized, including a structural study of 2,6-tert-butylbenzo[1,2-d;4,5-d']bisoxaphosphole. Quantum yields for photoluminescence were determined for a series of compounds. These materials feature bona fide P horizontal lineC p-p pi bonds suitable for conjugated materials having phosphorus as a participatory atom and can thus "photocopy" the properties of other conjugated organic molecules.
RESUMO
The novel organophosphorus-containing lithium salt Li(THF)[(C(2)O(4))B(O(2)PPh(2))(2)] (1; THF = tetrahydrofuran) was synthesized and characterized using a variety of spectroscopic techniques. An X-ray structural analysis on crystals of 1 grown from THF reveals a dimeric structure [Li(THF)(C(2)O(4))B(O(2)PPh(2))(2)](2)·THF, whereby the two units of 1 are bridged via P-O···Li interactions. Compound 1 displays high air and water stability and is also thermally robust, properties needed of electrolytes for their possible use as electrolytes and/or additives in lithium-ion battery applications.
RESUMO
Hydrogen bonding plays a critical role in maintaining order and structure in complex biological and synthetic systems. N-heterocyclic carbenes (NHCs) represent one of the most versatile tools in the synthetic chemistry toolbox, yet their potential as neutral carbon hydrogen bond acceptors remains underexplored. This report investigates this capability in a strategic manner, wherein carbene-based hydrogen bonding can be assessed by use of ditopic NH-containing molecules. N-H bonds are unique as there are three established reaction modes with carbenes: non-traditional hydrogen bonding adducts (X-Hâ¯:C[double bond splayed right]), salts arising from proton transfer ([H-C[double bond splayed right]]+[X]-), or amines from insertion of the carbene into the N-H bond. Yet, there are no established rules to predict product distributions or the strength of these associations. Here we seek to correlate the hydrogen bond strength of symmetric and asymmetric ditopic secondary amines with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr, a representative NHC). In symmetric and asymmetric ditopic amine adducts both the solid-state (hydrogen bond lengths, NHC interior angles) and solution-state (1H Δδ of NH signals, 13C signals of carbenic carbon) can be related to the pK a of the parent amine.
RESUMO
The diphosphene Mes*P=Mes* (Mes* = 2,4,6-tri-tert-butylphenyl; 1) reacted with 1 or 2 equiv of Au(tht)Cl (tht = tetrahydrothiophene) to produce the stable monoaurated adduct Mes*{AuCl}P=PMes* (2) or diaurated adduct Mes*{AuCl}P=P{AuCl}Mes* (3) respectively. The products were characterized by X-ray crystallography, UV-visible, IR, Raman, and multinuclear NMR spectroscopies, as well as by density functional theory calculations. The crystallographic and Raman spectroscopic data provide physical evidence that the P=P bond grows shorter and increases in strength upon auration; these observations are further examined by DFT calculations for a series of model compounds CH(3){AuCl}(n)P=P{AuCl}(n')CH(3) 1'-3' (n, n' = 0 or 1). Compounds 1-3 represent a rare series of crystallographically characterized diphosphenes bearing zero, one, or two AuCl units on each phosphorus atom, allowing for a systematic analysis of the impact of Lewis acids on the phosphorus-phosphorus double bond.
Assuntos
Compostos Organoáuricos/química , Fosfinas/química , Fósforo/química , Simulação por Computador , Cristalografia por Raios X , Ouro/química , Modelos Químicos , Modelos Moleculares , Conformação MolecularRESUMO
A new N,N'-bidentate ligand, 2-(3-isobutoxyanilino)pyridine (H(i)BuOap), was introduced and used as the ancillary ligand to support highly soluble diruthenium compounds. Thus, the new compounds Ru(2)((i)BuOap)(4)Cl (1), Ru(2)((i)BuOap)(4)(C[triple bond]CPh) (2), Ru(2)((i)BuOap)(4)(C[triple bond]CPh)(2) (3), and Ru(2)((i)BuOap)(4)(C[triple bond]CSi(i)Pr(3)) (4) were prepared and characterized by both voltammetric and spectroscopic methods, and their physical properties were found to be quite similar to those of the previously reported Ru(2)(ap)(4)-based compounds. The spectroscopic properties of both anionic and cationic derivatives of compounds 2 and 3 were examined with spectroelectrochemistry. Density functional theory calculations performed on model compounds of 2 and 3 provide an in-depth picture of the electronic structures of Ru(2)(ap)(4)-based alkynyl compounds and assignment of the observed electronic transitions.
RESUMO
Aryl diphosphenes (Ar-P=P-Ar) possess features that may make them useful in photonic devices, including the possibility for photochemical E-Z isomerization. Development of good models guided by computations is hampered by poor correspondence between predicted and experimental UV/vis absorption spectra. A hypothesis that the phenyl twist angle (i.e., PPCC torsion) accounts for this discrepancy is explored, with positive findings. DFT and TDDFT (B3LYP) were applied to the phenyl-P=P-phenyl (Ph-P=P-Ph) model compound over a range of phenyl twist angles, and to the Ph-P=P-Ph cores of two crystallographically characterized diphosphenes: bis-(2,4,6-tBu(3)C(6)H(2))-diphosphene (Mes*-P=P-Mes*) and bis-(2,6-Mes(2)C(6)H(3))-diphosphene (Dmp-P=P-Dmp). A shallow PES is observed for the model diphosphene: the full range of phenyl twist angles is accessible for under 5 kcal/mol. The Kohn-Sham orbitals (KS-MOs) exhibit stabilization and mixing of the two highest energy frontier orbitals: the n(+) and pi localized primarily on the -P=P- unit. A simple, single-configuration model based upon this symmetry-breaking is shown to be consistent with the major features of the measured UV/vis spectra of several diphosphenes. Detailed evaluation of singlet excitations, transition energies and oscillator strengths with TDDFT showed that the lowest energy transition (S(1) <-- S(0)) does not always correspond to the LUMO <-- HOMO configuration. Coupling between the phenyl rings and central -P=P- destabilizes the pi-pi* dominated state. Hence, the S(1) is always n(+)-pi* in nature, even with a pi-type HOMO. This coupling of the ring and -P=P- pi systems engenders complexity in the UV/vis absorption region, and may be the origin of the variety of photobehaviors observed in diphosphenes.
Assuntos
Derivados de Benzeno/química , Fosfinas/química , Teoria Quântica , Simulação por Computador , Modelos Químicos , FotoquímicaRESUMO
The photophysical properties of a series of heteroatom substituted indoles are explored to identify chemical means to control their emissive activity. In particular, we consider impacts of changes in the conjugated backbone, where the CâN bonds of benzoxazoles are replaced by CâP bonds (benzoxaphospholes). The effects of extending the π-conjugation, incorporating various secondary heteroatoms (X-CâP), and enforcing planar rigidity are also examined. Our computational analysis explains the higher fluorescence efficiency observed with extended π-conjugation and highlights the importance of maintaining molecular planarity at both ground- and emissive-state geometries.
RESUMO
The reaction of magnesium chloride with two equivalents of sodium phosphaethynolate, Na[OCP]·(dioxane)2.5 (1), yields a magnesium diphosphaethynolate complex, [(THF)4Mg(OCP)2] (3). The formation of compound 3 goes through a monosubstituted chloromagnesium phosphaethynolate Mg(OCP)Cl (2). The structure of 3 was determined via a single crystal X-ray diffraction study. For comparison, we also report the structure of a monomeric sodium phosphaethynolate complex, [Na(OCP)(dibenzo-18-crown-6)] (4).
RESUMO
Reaction of the zirconium-benzyne complex [Cp2Zr(PMe3)(C6H4)] with sodium phosphaethynolate, Na[OCP], affords a zircono-phosphaalkene complex. Notably, unlike reactions of other transition metal complexes with Na[OCP] that yield the products of simple salt metathesis, this transformation represents novel Na[OCP] insertion chemistry and formation of an unusual solid state coordination polymer. The polymer is disrupted upon addition of Me3SiCl to afford a silyl-capped dimer that retains the zirconophosphaalkene functionality. Protonation of either form of zirconophosphaalkenes results in the formation of benzoylphosphine, PhC([double bond, length as m-dash]O)PH2.
RESUMO
The reaction of the chloroimidazolium chloride salt, [NHC-Cl][Cl], NHC = C{N(2,6-iPr2C6H3)CH}2 (1) with two equivalents of sodium phosphaethynolate, Na[OCP]·(dioxane)2.5, results in the formation of NHC-{cyclo-(CO)-P2-C(O)} (2) and NHC-P2-C(O)-NHC (3). Notably, in the presence of free NHC ligand, compound 2 converts to compound 3via extrusion of CO at elevated temperatures. The nature of the bonding in these complexes was probed computationally and spectroscopically.
RESUMO
[reaction: see text] A new thiouronium-based reagent for the synthesis of 2-pyridinethiol esters under non-nucleophilic conditions from the corresponding carboxylic acids was developed. The resulting procedure enables the preparation of previously unavailable alpha,beta-unsaturated 2-pyridinethiol esters as well as their aliphatic and aromatic counterparts.