Steric Influence Research Articles

Investigation of the complete encapsulation process of the noble gases by cryptophanes.

Based on DFT calculations (ωB97XD/def2-SVP/SVPfit), the ability and mechanism of noble gas encapsulation by series of cryptophanes were investigated. The focus was set to study the influence of different functionalization groups placed at the "gates" of cryptophanes cavity entrance by which the energy criteria were chosen as a main indicator for selective encapsulation of noble gases. Chosen functionalization groups were CH3, OCH3, OH, NH2, and Cl, and the encapsulation process of these cryptophanes was compared to a cryptophane without any functionalization group on its outer rim. Those groups were selected based on their different chemical properties and based on their size which will subsequently put additional steric restrictions on the cavity entrance. Chosen functionalization groups, beside their steric influence on the energy barrier magnitude, influence also the gating process through its chemical nature by which they can put an additional stabilization on noble gases encapsulation transition states enhancing the encapsulation process. Objective of this study was clearly to get better insights on the influence of those functional groups on the whole encapsulation process of noble gases. Large-size noble gases (Xe and Rn) from all noble gases are best accommodated in the cavities of selected cryptophanes, on the other hand these noble gases require to pass the highest energy barrier through the gating process. From the series of investigated cryptophanes, the cryptophane with the OCH3 functionalization group has been identified as the one with the best capabilities to host investigated noble gases, but on the other side this cryptophane puts the highest energy criteria required for the previous gating process.

Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al-Salen Complexes.

The origin of stereocontrol in ring opening polymerization (ROP) of racemic lactide (rac-LA) promoted by achiral aluminium-based catalysts has been explained through DFT calculations combined with a molecular descriptor (%VBur) and the activation strain model (ASM-NEDA) analysis. The proposed chain end control (CEC) model suggests that the ligand framework adopts a chiral configuration mimicking the enantiomorphic site control (ESC) while also incorporating control of the last inserted monomer unit. It is found that the ligand wrapping mode around the aluminium centre is dictated by the monomer configuration (R,R-LA and S,S-LA). A good correlation with experimental data is achieved only when accounting for the ligand dynamic features and its steric influences, as highlighted by %VBur steric maps and ASM-NEDA analysis. Understanding the ESC and CEC interplay is an important target for obtaining stereoselective ROP polymerization for the synthesis of biodegradable materials with tailored properties.

Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores.

ConspectusFor the past 11 years, a dedicated effort in our research group focused on fundamentally advancing the photophysical properties of cuprous bis-phenanthroline-based metal-to-ligand charge transfer (MLCT) excited states. We rationalized that, by gaining control over the numerous factors limiting the more widespread use of CuI MLCT photosensitizers, they would be readily adopted in numerous light-activated applications given the earth-abundance of copper and the extensive library of 1,10-phenanthrolines developed over the last century. Significant progress has been achieved by recognizing valuable structure-property concepts developed by other researchers in tandem with detailed ultrafast and conventional time-scale investigations, in-silico-inspired molecular designs to predict spectroscopic properties, and applying novel synthetic methodologies. Ultimately, we achieved a plateau in exerting cooperative steric influence to control CuI MLCT excited state decay. This led to combining sterics with π-conjugation and/or inductive electronic effects to further exert control over molecular photophysical properties. The lessons gleaned from our studies of homoleptic complexes were recently extended to heteroleptic bis(phenanthrolines) featuring enhanced visible light absorption properties and long-lived room-temperature photoluminescence. This Account navigates the reader through our intellectual journey of decision-making, molecular and experimental design, and data interpretation in parallel with appropriate background information related to the quantitative characterization of molecular photophysics using CuI MLCT chromophores as prototypical examples.Initially, CuI MLCT excited states, their energetics, and relevant structural conformation changes implicated in their photophysical decay processes are described. This is followed by a discussion of the literature that motivated our research in this area. This led to our first molecular design in 2013, achieving a 7-fold increase in excited state lifetime relative to the current state-of-the-art. The lifetime and photophysical property enhancement resulted from using 2,9-branched alkyl groups in conjunction with flanking 3,8-methyl substituents, a strategy we adapted from the McMillin group, which was initially described in the late 1990s. Applications of this newly conceived chromophore are presented in solar hydrogen-producing photocatalysis, photochemical upconversion, and photosensitization of [4 + 4] anthracene dimerization of potential interest in thermal storage of solar energy in metastable intermediates. Ultrafast transient absorption and fluorescence upconversion spectroscopic characterization of this and related CuI molecules inform the resultant photophysical properties and vice versa, so the most comprehensive structure-property understanding becomes realized when these experimental tools are collectively utilized to investigate the same series of molecules. Computationally guided structural designs generated newly conceived molecules featuring visible light-harvesting and 2,9-cycloalkane substituted complexes. The latter eventually produced record-setting excited state lifetimes in molecules leveraging both cooperative steric influence and electronic inductive effects. Using photoluminescence data from structurally homologous CuI MLCT excited states collected over 44 years, an energy gap correlation successfully modeled the data spanning a 0.3 eV emission energy range. Finally, a new research direction is revealed detailing structure-photophysical property relationships in heteroleptic CuI phenanthroline chromophores that are photoluminescent at room temperature.

Mapping Electrophile Chemoselectivity in DalPhos/Nickel N‐Arylation Catalysis: The Unusual Influence of Remote Sterics

We disclose herein our evaluation of competitive (hetero)aryl‐X (X: Br > Cl > OTf) reactivity preferences in bisphosphine/Ni‐catalyzed C‐N cross‐coupling catalysis, using furfurylamine as a prototypical nucleophile, and employing DalPhos and DPPF as representative ancillary ligands with established efficacy. Beyond this general (pseudo)halide ranking, other intriguing structure‐reactivity trends were noted experimentally, including the unexpected observation that bulky alkyl (e.g., R = tBu) substitution in para‐R‐aryl‐X electrophiles strongly discourages (pseudo)halide reactivity relative to smaller substituents (e.g., nBu, Et, Me), despite being both remote from, and having a similar electronic influence on, the reacting C‐X bond; such effects on nickel oxidative addition have not been documented previously and were not observed in our comparator reactions presented herein involving palladium. Density functional theory modeling of such PhPAd‐DalPhos/Ni‐catalyzed C‐N cross‐couplings revealed the origins of competitive turnover of C‐Br over C‐Cl, and possible ways in which bulky para‐alkyl substitution might discourage net electrophile uptake/turnover, leading to inversion of halide selectivity.

Steric Influences on Chain Microstructure in Palladium-Catalyzed α-Olefin (Co)polymerization: Unveiling the Steric-Deficient Effect.

This study addresses the challenge of controlling branching density and branch-type distribution in late-transition-metal-catalyzed chain walking polymerizations. We explored α-diimine Pd(II) complexes with incrementally increased ortho-aryl sterics for long-chain α-olefin (co)polymerization. Pd0-Pd3 catalysts, which feature gradually increased ortho-aryl sterics and at least one small CH3 substituent, exhibited similar 2,1-insertion fractions (44-50%), polymer branching densities (55-63/1000C), and melting temperatures (26-28 °C). In contrast, Pd4 with bulky ortho-aryl sterics covering all sides demonstrated a significant increase in 2,1-insertion fractions up to 82%, leading to "PE-like" polymers with high melting temperatures (Tm > 111 °C). This abrupt change in polymerization behavior, termed the "steric-deficient effect", contrasts with the gradual changes observed in similar Ni(II) systems that we reported previously. Furthermore, due to the rapid chain walking ability of Pd(II) catalysts in long-chain α-olefin (co)polymerization, these catalysts favor the production of polyolefins with higher proportions of methyl branches compared to those produced by Ni(II) catalysts. Particularly, these Pd(II) catalysts are capable of synthesizing functionalized semicrystalline copolymers by copolymerizing 1-octene with a variety of polar comonomers, thereby significantly altering the surface properties of the materials.

Influence of Chemical Structures on E-Beam Lithography Performance of Polysilsesquioxanes.

Hydrogenated silsesquioxane (HSQ) is a key inorganic electron beam resist, celebrated for its sub-10 nm resolution and etching resistance, but it faces challenges with stability and sensitivity. Our innovative study has comprehensively assessed the lithographic performance of three functionalized polysilsesquioxane (PSQ) resist series─olefins, halogenated alkanes, and alkanes─under electron beam lithography (EBL). We discovered that the addition of olefin groups, such as in the HMP-30 formulation with 30% propyl acrylate, remarkably increased the sensitivity to 0.6 μC/cm2. The inclusion of halogenated aromatic and hydrogen-substituted methyl groups further enhanced sensitivity and contrast, with HClBN-50 achieving a 22.9 nm resolution pattern. At the same time, the storage of PSQ resists was significantly improved compared to commercial HSQ with increasing alkane group content. Crucially, our research has unveiled the lithography reaction mechanism, highlighting how group encapsulation and steric hindrance influence PSQ performance. This insight is groundbreaking, offering a deeper understanding of the molecular structure-performance relationship and laying the groundwork for developing next-generation electron beam resists with superior sensitivity, resolution, and contrast for microelectronics manufacturing.

Expanding the Horizons of Suzuki Reactions: Pd‐PEPPSI–Mediated Traditional and Decarbonylative Couplings With Diverse Assure Analogues

ABSTRACTWe have developed a highly efficient, ligand‐free Suzuki–Miyaura cross‐coupling protocol employing our lab‐prepared air and moisture‐stable Pd‐PEPPSI catalysts. The reaction of ethyl 2‐{4‐[(6‐chloroquinoxalin‐2‐yl)oxy]phenoxy}propionate (Assure) with various boronic acids afforded both traditional and decarbonylative coupling products in high yields. The catalyst's steric influence was assessed computationally using %Vbur calculations. The decarbonylative coupling pathway proved more efficient than the traditional Suzuki–Miyaura coupling under these conditions. Additionally, regioselectivity studies have been conducted on a variety of Assure analogues. This method excels in efficiency, requiring minimal catalyst, moderate temperatures, and rapid reaction completion.

Steric Engineering of Rotaxane Catalysts: Benefits and Limits of Using the Mechanical Bond in Catalyst Design.

The mechanical bond is emerging as a novel design element in catalyst development. Here, we report a series of 1,1´‑binaphthyl-2,2´-diol (BINOL) based catalysts in which the number of interlocked macrocycles is varied. Unsurprisingly, the macrocycles have a profound steric influence on the catalytic performance of these molecules. However, in the enantioselective transformations examined, the macrocycles are detrimental to catalyst stereoselectivity whereas in lactide polymerization, they increase the molecular weight of the polymeric product.

Synthesis and Characterization of Coordination Compounds with Novel Ligands: Implications for Material Science

Coordination compound are any of a class of substances with produced plans where a central metallic particle is encircled by non-metal elements or social assemblies of particles, termed ligands. A basic use of coordination compounds is their use as motivations, which effectively change the speed of designed responses. This study researches the mix and depiction of coordination compounds incorporating novel ligands, with an accentuation on their ideas for material science. Coordination compounds, outlined by the coordination of a central metal atom or molecule with various ligands, are crucial for an extent of engineered and present day cycles. In this investigation, we detail the mix of a couple of coordination compounds featuring as of late made ligands. These ligands are planned to give express electronic and steric influences, smoothing out the introduction of the ensuing edifices.

Synthesis of 9-(substituted phenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonates: Effects of the leaving group on chemiluminescent properties.

Various 9-(substituted phenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonates possessing electron-withdrawing substituents have been synthesized. The effect of substituents on the stability of the acridinium esters (AEs) at various temperatures in different buffers and the chemiluminescent properties have been examined. There was little correlation between the chemiluminescent properties of AEs and the pKa values of their associated phenols, but the steric effects of the ortho-substituents in the phenoxy group, as well as their electron-withdrawing natures, seem to play an important role in determining the properties. In general, when two identical substituents are present in the 2- and 6-positions, the compound is significantly more stable than when only a single substituent is present, presumably because of greater steric hindrance from the second group. The exception is the 2,6-difluorophenyl ester, which is less stable than the 2-fluorophenyl ester, presumably because the fluoro group is small. Addition of a third electron-withdrawing substituent at the 4-position, where it has no steric influence, typically increases susceptibility to decomposition. The presence of a nitro group has a significant destabilizing effect on AEs. Of the AEs studied, the 4-chlorophenyl ester showed the greatest chemiluminescent yield, while the 2-iodo-6-(trifluoromethyl)phenyl ester group showed the greatest stability in low pH buffers.

A Bis-Porphyrin Cavitand Breathing-In to Constrict Bucky Balls.

Bis-porphyrin cages have long been exploited to bind fullerenes selectively for various applications. The major consideration for an effective binding here had been the cavity size. Herein, we structurally demonstrate that a bis-Ni-porphyrin cavitand having even a smaller cavity can host a larger fullerene by a breathing and ruffling mechanism. It has also been shown that both the electronic and steric influence at the meso- positions of the porphyrin in fact dictate the binding character. The smaller cavity of 2NiD exhibits preferential binding for C70 over C60; however, surprisingly, the larger cavities in 2HD and 2NiTD display stronger affinities for C60 over the larger fullerene. We show here that the structural elasticity infused both by the metalloporphyrins and the connecting bridges play a major role in directing the binding. These conclusions have adequately been supported by structural and spectroscopic investigations. Additionally, the suitability of one of the conjugates for photoinduced charge-separation has been investigated using ultrafast transient absorption measurements. 2NiD⊃C60 has a charge separation timescale of ~0.8 ps, while charge recombination occurs at a longer timescale of ~920 ps.

Syntheses and reactivities of polymethylated ferrocenes: The effect of methylation upon electrophilic addition

A series of ferrocene derivatives with three, four, five, six and seven methyl group substituents has been prepared and characterized by multinuclear NMR, high resolution mass spectrometry and elemental analyses. Chemical oxidation of heptamethylferrocene with silver tetrafluoroborate produced paramagnetic heptamethylferricenium tetrafluorborate and the structure of one isomer of [C5Me4HFeC5Me3H2][BF4] was determined by single crystal X-ray diffraction. Electrochemical studies of the entire series of iron sandwich compounds from ferrocene to decamethylferrocene reveal a highly linear shift of the reversible half-wave potential (E1/2) for the FeIII/FeII couple such that each additional methyl group lowers E1/2 by an average of 54 mV. A new triple-decker complex has been synthesized by the addition of a ruthenium electrophile, [Cp*Ru(NCMe)3][PF6], (Cp* = C5Me5) to heptamethylferrocene, Me7FcH. While previous work established that reactions between [Cp*Ru(NCMe)3][PF6] and ferrocene derivatives with eight or more methyl group substituents readily form bimetallic complexes, reactions with ferrocene derivatives with six or fewer methyl groups brought about ring abstraction and afforded only monometallic products. Thus it may be concluded that there is a “tipping point” in the series of polymethylated ferrocenes such that the electron donating ability and/or steric influence of seven methyl groups is just sufficient to stabilize a ruthenium-iron tripledecker complex.

Metal-Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation.

The local environment of a metal active site plays an important role in affecting the catalytic activity and selectivity. In recent studies, tailoring the behavior of a molybdenum-based active site via modulation of the first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise from these modifications is nontrivial, especially in heterogeneous systems. To this end, the tunability of metal-organic frameworks (MOFs) makes them promising scaffolds for controlling the coordination sphere of a heterogeneous, catalytically active metal site while offering additional attractive features such as crystallinity and high porosity. Herein, we report a variety of MOF-supported Mo species, which were investigated for catalytic thioanisole oxidation to methyl phenyl sulfoxide and/or methyl phenyl sulfone using tert-butyl hydroperoxide (tBHP) as the oxidant. In particular, MOFs of contrasting node architectures were targeted, presenting a unique opportunity to investigate the stereoelectronic control of Mo active sites in a systematic manner. A Zr6-based MOF, NU-1000, was employed along with its sulfated analogue Zr6-based NU-1000-SO4 to anchor a dioxomolybdenum species, which enabled examination of support-mediated active site polarizability on catalytic performance. In addition, a MOF containing a mixed metal node, Mo-MFU-4l, was used to probe the stereoelectronic impact of an N-donor ligand environment on the catalytic activity of the transmetalated Mo center. Characterization techniques, including single crystal X-ray diffraction, were concomitantly used with reaction time course profiles to better comprehend the dynamics of different Mo active sites, thus correlating structural change with activity.

All-Atom Molecular Dynamics Simulations of Uncharged Linear Polymer Bottlebrushes: Effect of the Brush Sizes and the Number of Side-Chain Monomers.

Bottlebrush polymers (BBPs), characterized by grafted polymer side chains on linear backbone polymer chain, have emerged as a unique and versatile class of macromolecules with extensive applications in the fields of material science, electronics, battery materials, self-healing technology, etc. In this paper, we employ all-atom molecular dynamics (MD) simulations to present a comprehensive study of poly(methyl methacrylate)-g-poly(2-ethyl-2-oxazoline) (PMMA-g-PEtOx) BBP and its structural and hydration properties for varying number of backbone monomers (NBB) and side chain monomers (NSC), as well as properties of water molecules supported by the BBP. We find that the radius of gyration follows a scaling of Rg ∼NSC0.36 for smaller grafts and Rg ∼ NSC0.52-0.58 for longer grafts. We also find that the overall shape of the bottlebrush goes from a rod to sphere-like shape with the increase in NSC. Both the hydration per side chain monomer and hydrogen bonds (HBs) per oxygen and nitrogen of the side chain monomer reduce with an increase in NSC, caused by a corresponding enhancement in localization of the side chain monomers in the interior of the BBP. Furthermore, steric influences ensure the number of water-oxygen HBs is much more than the number of water-nitrogen HBs (with oxygen and nitrogen atoms belonging to the monomer side chains). Also, the BBP-supported water molecules demonstrate two distinctly ordered domains with one more structured and one less structured. The more structured domain disappears with an increase in NSC that causes more side chain monomers to localize in the interior of the BBPs. Finally, we observe that despite the highly negative partial charges of the oxygen and nitrogen atoms (of the side chain monomers), the dipole orientation distributions of water molecules around these atoms exhibit the presence of a neutral environment rather than an anionic environment. Overall, we anticipate that our study will generate significant interest in probing the various BBP systems in greater atomistic detail.

Decoration of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) with N-oxides increases the T1 relaxivity of Gd-complexes.

High complex stability and longitudinal relaxivity of Gd-based contrast agents are important requirements for magnetic resonance imaging (MRI) because they ensure patient safety and contribute to measurement sensitivity. Charged and zwitterionic Gd3+-complexes of the well-known chelator 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) provide an excellent basis for the development of safe and sensitive contrast agents. In this report, we describe the synthesis of DOTA-NOx, a DOTA derivative with four N-oxide functionalities via "click" functionalization of the tetraazide DOTAZA. The resulting complexes Gd-DOTA-NOx and Eu-DOTA-NOx are stable compounds in aqueous solution. NMR-spectroscopic characterization revealed a high excess of the twisted square antiprismatic (TSAP) coordination geometry over square antiprismatic (SAP). The longitudinal relaxivity of Gd-DOTA-NOx was found to be r1=7.7 mm-1 s-1 (1.41 T, 37 °C), an unusually high value for DOTA complexes of comparable weight. We attribute this high relaxivity to the steric influence and an ordering effect on outer sphere water molecules surrounding the complex generated by the strongly hydrated N-oxide groups. Moreover, Gd-DOTA-NOx was found to be stable against transchelation with high excess of EDTA (200 eq) over a period of 36 h, and it has a similar in vitro cell toxicity as clinically used DOTA-based GBCAs.

Reactive Vapor-Phase Inhibitors for Area-Selective Depositions at Tunable Critical Dimensions.

Area-selective depositions (ASD) take advantage of the chemical contrast between material surfaces in device fabrication, where a film can be selectively grown by chemical vapor deposition on metal versus a dielectric, for instance, and can provide a path to nontraditional device architectures as well as the potential to improve existing device fabrication schemes. While ASD can be accessed through a variety of methods, the incorporation of reactive moieties in inhibitors presents several advantages, such as increasing thermal stability and limiting precursor diffusion into the blocking layer. Alkyne-terminated small molecule inhibitors (SMIs)─propargyl, dipropargyl, and tripropargylamine─were evaluated as metal-selective inhibitors. Modeling these SMIs provided insight into the binding mechanism, influence of sterics, and complex polymer network formed from the reaction between inhibitors consisting of alkene, aromatic, and network branchpoints. While a significant contrast in the binding of the SMIs on copper versus a dielectric was observed, residual amounts were detected on the dielectric surfaces, leading to variable ALD growth rates dependent on pattern-critical dimensions. This behavior can be controlled and utilized to direct film growth on patterns only above a critical threshold dimension; below this threshold, both the dielectric and metal features are protected. This method provides another design parameter for ASD processes and may extend its application to broader-ranging device fabrication schemes.

Characterization of the Ligand Properties of Donor-stabilized Pnictogenyltrielanes.

A general synthesis and the characterization of novel alkyl-substituted NHC-stabilized pnictogenylboranes NHC ⋅ BH2 ER2 (NHC=N-heterocyclic carbene, E=P, As; R2 =Me2 , Ph2 , t BuH, Cy2 , (SiMe3 )2 ) are reported. These compounds were reacted with Ni(CO)4 to the corresponding complexes of the type [(NHC ⋅ BH2 ER2 )Ni(CO)3 ] to determine their donor strength by Tolman Electronic Parameters (TEPs) and their steric demand as ligands compared to classical phosphines, superbasic phosphines and other commonly applied donor systems. The results show that the NHC-stabilized pnictogenyltrielanes can be considered as being highly basic, while their steric influence depends strongly on the organic residues as well as the donor attached to the {BH2 } moiety. Although weaker than commonly used superbasic phosphines, the donor strength of pnictogenyltrielanes in general can be classified as of similar strength as NHCs. The steric and electronic properties can easily be modified by alkyl substitution as evident from the TEP trends.

Reactivity of low-valent nickel carbonyl species supported by acridane based PNP ligands towards iodoalkanes.

Nickel monocarbonyl species with Ni(I) and Ni(0) have been synthesized and fully characterized by employing an acriPNP-Ph pincer ligand having a -C(Ph)2- bridge moiety to tether two aromatic rings. To see the effect of the bridge moiety, these complexes were structurally compared with the previously studied nickel complexes supported by PNP and acriPNP-Me ligands and methylation of the nickel carbonyl species was particularly investigated. Since a Ni(I)-CO species is known to be one of the key intermediates during the C-C coupling reaction to give an acetyl species, according to the paramagnetic mechanism of acetyl coenzyme A synthase (ACS), their reactivity toward MeI has been examined. Methylation of a nickel(I)-CO species reveals enhanced C-C coupling when both acriPNP-Me and acriPNP-Ph ligands were used. According to spin density analysis calculated by density functional theory, all Ni(I)-CO species reveal similar spin density at nickel and the carbon atom of CO. X-ray crystallographic data suggest that the corresponding selectivity may be related to the steric influence. For both (acriPNP-Ph)Ni-CO (2) and (acriPNP-Me)Ni-CO (2'), the nickel(I) site is sterically well protected, leading to selective interaction with a methyl radical to give a nickel acyl product. Steric influence was marginally observed when an anionic {(acriPNP-R)Ni-CO}- (R = Me or Ph) species reacted with MeI. The corresponding C-C coupled product was also observed from the methylation of nickel(0)-CO species.

Steric influence and controlled dynamic process in a chiral square planar nickel(ii) complex supported by a dipyrromethane-based NNNN tetradentate ligand

The intra-ligand congestion in a square planar nickel(ii) complex of a dipyrromethane-based ligand decides helical chirality and the pair of enantiomers exists in a dynamic equilibrium in solution. A similar complex without congestion is achiral.

Effect of the extended π-surface and N-butyl substituents of imidazoles on their reactivity, electrochemical behaviours and biological interactions of corresponding Pt(ii)-CNC carbene complexes: exploring DFT and docking interactions

The extended π surface and the N-butyl arms on the bis(3-methylimidazolium-1-yl)pyridine ligand cause prominent σ-inductive effect and steric influences on the complexes which stabilises the metal centres which leads to damping in their reactivity.