Small HOMO-LUMO Gap Research Articles

One-Pot Divergent Synthesis of a 13-Ring Triquinone and its Facile Conversion to a [4.4.4]Tridecastarphene.

Acenes are notable for their optoelectronic properties and applications in organic electronics. Starphenes are structurally related molecules possessing three acene arms that radiate linearly from a central benzene ring (i. e., linearly annellated triphenylenes). Large starphenes have been prepared using convergent syntheses involving transition metal catalyzed cyclotrimerizations of either preformed acenes or arynes. Here, we report a one-pot divergent synthesis of a 13-ring triquinone that is readily converted to a [4.4.4]tridecastarphene derivative. The one-pot procedure involves the sequential reactions of three 1,4-anthraquinones with o-quinodimethane derivatives that are generated sequentially from a stable, trisulfone precursor. The resulting [4.4.4]tridecastarphene derivative bearing p-(t-butyl)phenyl substituents was characterized by 1H NMR, 13C NMR and UV-vis spectroscopies, as well as mass spectrometry, cyclic voltammetry and differential pulse voltammetry. Theoretical and experimental studies reveal a relatively high-lying HOMO orbital (about -4.70 to -4.86 eV) and a relatively small HOMO-LUMO gap (2.1 eV), suggesting utility as a p-type organic semiconductor. Our [4.4.4]tridecastarphene derivative photooxidizes in a CH2Cl2 solution exposed to ambient light and air with a half-life of 150 minutes at room temperature, but shows no sign of degradation after 12 months in the solid-state. Our [4.4.4]tridecastarphene derivative also shows excellent solubility in a number of organic solvents including dichloromethane, chloroform and toluene, potentially enabling printed electronic applications.

Dye-Containing Polymers with π-Extened Diketopyrropyrrole Derivatives for Semi-Transparent Organic Photovoltaics.

Dye-containing polymers P1 (PEDPP-OT-BDT) and P2 (PEDPP-OT-BDTT) including a π-extended diketopyropyrrole (DPP) derivative and electron-rich thiophene fused ring units (4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b']dithiophene for P1 and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene for P2) were synthesized as narrow band gap dyes. A π-extended DPP (EDPP-OT-BrPh), fragment of the polymers P1 and P2, was obtained by extending the π-conjugation of DPP using Ru(III)-catalyzed C-H and N-H activation reported by Gońka et al. in 2019, exhibiting a high quantum yield (ϕem=0.84) and small HOMO-LUMO gap (Eg=1.69 eV) due to the spatial overlap of the HOMO and LUMO orbitals. The solubility of the π-extended DPP was improved by introducing four 2-octylthophene side chains around the periphery of the planer dye moiety, while maintaining the high planarity of the dye molecule, which is essential to the function of optoelectronic devices. As a result, P1 and P2, polymerized with the π-extended DPP and BDT derivatives, exhibit carrier mobility of approximately 10-5 cm2/Vs in organic field-effect transistors (OFETs). In bulk heterojunction (BHJ) solar cells with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), they demonstrate a power conversion efficiency (PCE) of 1.0 % with an average transmittance (AVTs) of around 60 %.

Carbodiphosphorane-Activated Distibene and Dibismuthene Dications.

Low-valent antimony and bismuth have emerged as novel platforms for achieving reversible small-molecule activation at main-group metals. Although various examples of oxidative addition reactions at monomeric Sb(I) and Bi(I) have been reported, the chemistry of the heavy group 15 Sb(I)═Sb(I)/Bi(I)═Bi(I) double bonds toward small molecules remains largely unexplored. In this study, we present a straightforward synthesis of distibene and dibismuthene dications coordinated with a neutral carbodiphosphorane (CDP) ligand. The nonbonding interactions between the occupied p-orbital at the CDP ligand and the π-bonding orbital of the Sb═Sb/Bi═Bi bonds yield compounds with exceptionally small HOMO-LUMO gaps. In addition, the reduction of steric hindrance compared to known neutral derivatives stabilized with bulky aryl groups allows for better accessibility of the double bonds. This high reactivity is demonstrated in the oxidative addition of distibene to diphenyldisulfide as well as in [2+2] cycloadditions to alkynes. Additionally, the Sb═Sb bond reversibly adds to 2,3-dimethylbutadiene in a [4+2] cycloaddition reaction.

Phenyl-urea chromophores: DFT insights into nonlinear optical enhancement

The present investigation has examined the nonlinear optical (NLO) responses of molecules based on phenyl-urea. The optimized geometries of complexes: (4-nitrophenyl) urea (PU1), 1-methyl-3-(4-nitrophenyl) urea (PU2), and 1,1-dimethyl-3-(4-nitrophenyl) urea (PU3) are extracted using M06–2X/6–311++ g (d, p) level of theory. The estimated nonlinear optical responses (NLO) of the compounds given are based on static and dynamic hyperpolarizabilities, which are reinforced by the dipole moment, polarizabilities, global reactivity parameters, HOMO-LUMO gap, molecular electrostatic potentials (MEP), and βvec. Comparing PU1, PU2, and PU3 to reference substances like urea and p-nitroaniline, a considerably higher NLO activity is estimated. Out of all the compounds, PU3 has the largest NLO response. Such a significant NLO reaction can be attributed to a small HOMO-LUMO gap and high charge transfer. Second-harmonic generation (SHG) and electro-optic Pockel's effect (EOPE) are being explored for dynamic NLO responses. These compounds that are bases of phenyl-urea exhibit a very significant quadratic nonlinear optical response.

Revisiting Artifacts of Kohn-Sham Density Functionals for Biosimulation.

We revisit the problem of unphysical charge density delocalization/fractionalization induced by the self-interaction error of common approximate Kohn-Sham (KS) density functional theory functionals on simulation of small to medium-sized proteins in a vacuum. Aside from producing unphysical electron densities and total energies, the vanishing of the HOMO-LUMO gap associated with the unphysical charge delocalization leads to an unphysical low-energy spectrum and catastrophic failure of most popular solvers for the KS self-consistent field (SCF) problem. We apply a robust quasi-Newton SCF solver [ Phys. Chem. Chem. Phys. 2024, 26, 6557] to obtain solutions for some of these difficult cases. The anatomy of the charge delocalization is revealed by the natural deformation orbitals obtained from the density matrix difference between the Hartree-Fock and KS solutions; the charge delocalization not only can occur between charged fragments (such as in zwitterionic polypeptides) but also involves neutral fragments. The vanishing-gap phenomenon and troublesome SCF convergence are both attributed to the unphysical KS Fock operator eigenspectra of molecular fragments (e.g., amino acids or their side chains). Analysis of amino acid pairs suggests that the unphysical charge delocalization can be partially ameliorated by the use of some range-separated hybrid functionals but not by semilocal or standard hybrid functionals. Last, we demonstrate that solutions without the unphysical charge delocalization can be located even for semilocal KS functionals highly prone to such defects, but such solutions have non-Aufbau character and are unstable with respect to mixing of the non-overlapping "frontier" orbitals. Caution should be exercised when unexpectedly small (or vanishing) HOMO-LUMO gaps and atypical SCF convergence patterns (e.g., oscillatory) are observed in KS DFT simulations in any context (bio or otherwise).

A Configurationally Stable Helical Indenofluorene.

We report the synthesis and study of the optoelectronic, magnetic, and chiroptical properties of a helically chiral diradicaloid based on dibenzoindeno[2,1-c]fluorene. The molecule shows a small HOMO-LUMO gap and a moderate singlet-triplet gap, which agrees with the results of DFT calculations. The helical structure of the compound, confirmed by X-ray diffraction, is configurationally stable, which allows the isolation of both enantiomers and the evaluation of the chiroptical properties (ECD).

'Passivated Precursor' Approach to All-Alkynyl-Protected Gold Nanoclusters and Total Structure Determination of Au130.

A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au22(C≡CR)18 (R=-C6H4-2-F), Au36(C≡CR)24, Au44(C≡CR)28, Au130(C≡CR)50, and Au144(C≡CR)60. These clusters can be well separated via column chromatography. The overall isolation yield of this series of clusters is 40 % (based on gold), which is much improved in comparison with previous approaches. It is notable that the molecular structure of the giant cluster Au130(C≡CR)50 is revealed, which presents important information for understanding the structure of the mysterious Au130 nanoclusters. Theoretical calculations indicated Au130(C≡CR)50 has a smaller HOMO-LUMO gap than Au130(S-C6H4-4-CH3)50. This facile and reliable synthetic approach will greatly accelerate further studies on all-alkynyl-protected gold nanoclusters.

Adsorption Behaviour of Pb and Cd on Graphene Oxide Nanoparticle from First-Principle Investigations.

Graphene oxide (GO) is considered as a promising adsorbent material for the removal of metal from aqueous environments. Here, we have used the density functional theory (DFT) approach and a combination of parameters to characterise the interactions of GO with lead (Pb) and cadmium (Cd), i.e., typical harmful metals often found in water. Our model systems consist of a singly and doubly adsorbed neutral (Pb0, Cd0) and charged (Pb2+, Cd2+) atoms adsorbed on the GO nanoparticle of the chemical formula C30H14O15. We show that a single charged metal ion binds more strongly than a neutral atom of the same type. Moreover, to determine the possibility of multiple adsorptions of the GO nanoparticle, two metal atoms of the same species were co-adsorbed on its surface. We found a site-dependent adsorption energy such that when two atoms of the same specie are adsorbed at sites Si and Sj, the binding energy per atom depends on whether one of the two atoms is adsorbed firstly on the Si or Sj sites. Furthermore, the binding energy per atom for the two co-adsorbed atoms of the same specie (i.e., neutral or charged) is less than the binding energy of a singly adsorbed atom. This suggests that atoms may become less likely to be adsorbed on the GO nanoparticle when their concentration increases. We adduce the origin of this observation to be interplay between the metal-metal interaction on the one hand and GO-metal on the other, with the former resulting in less binding for the charged adsorbed metals in particular, due to repulsive interaction between two positively charged ions. The frontier molecular orbitals analysis and the calculated global reactivity descriptors of the respective GO-metal complexes revealed that all the GO-metal complexes have a smaller HOMO-LUMO gap (HLG) relative to that of pristine metal-free GO nanoparticle. This may indicate that although the GO-metal complexes are stable, they are less stable compared to metal-free GO nanoparticles. The negative values of the chemical potentials obtained for all the GO-metal complexes further confirm their stability. Our work differs from previous experimental studies in that those lacked details of the interaction mechanisms between GO, Pb and Cd, as well as previous theoretical studies which used limited numbers of parameters to characterise the GO-metal interactions. Rather, we present a set of parameters or descriptors which provide comprehensive physical and electronic characterisation of GO-metal systems as obtained via the DFT calculations. These parameters, along with those reported in previous studies, may find applications in rational design and high-throughput screening of graphene-based materials for water purification, as an example.

Kinetically stabilized 1,3-diarylisobenzofurans and the possibility of preparing large, persistent isoacenofurans with unusually small HOMO-LUMO gaps.

DFT calculations demonstrate that an isoacenofuran of any size possesses a smaller HOMO-LUMO gap than the corresponding acene bearing an isoelectronic π-system (i.e., the same total number of rings). Isoacenofurans show limited stability due in part to the highly reactive 1,3-carbons of the furan ring. Both 1,3-dimesitylisobenzofuran and 1,3-di(2',4',6'-triethylphenyl)isobenzofuran, each bearing sterically congesting ortho-alkyl groups on their phenyl substituents, have been synthesized and shown to adopt non-planar conformations with the ortho-alkyl groups located above and below the most reactive 1,3-carbons of the furan ring. These bulky substituents provide a strong measure of kinetic stabilization. Thus, 1,3-dimesitylisobenzofuran and 1,3-di(2',4',6'-triethylphenyl)isobenzofuran are significantly less reactive than 1,3-diphenylisobenzofuran toward the strong dienophiles DMAD and acrylonitrile. The insights gained here suggest that the synthesis of large, persistent, kinetically stabilized isoacenofurans with unusually small HOMO-LUMO gaps is achievable. As such, these molecules deserve increased attention as potential p-type organic semiconductors.

Mechanisms for the separation of Li+ and Mg2+ from salt lake brines using TBP and TOP systems

The tributyl phosphate (TBP)/FeCl3 system has been widely used for lithium extraction from high‑magnesium salt lakes. However, at high TBP concentrations, the Li/Mg selectivity is significantly lower. This study revealed that at high TBP concentrations, TBP alone extracted Mg2+ to form MgCl2·6TBP as the main product, thus affecting the extraction efficiency of Li+. On this basis, a neutral phosphate with long carbon chains, trioctyl phosphate (TOP), was used to replace TBP. The separation capacity and extraction mechanism of the TOP/FeCl3 system were studied, and density functional theory (DFT) calculations were employed to model the cationic complexes of the TOP and TBP systems. The results showed that in the presence of FeCl3, the extraction efficiency of Li+ (ELi) reached 91 %, and the Li/Mg separation factor (βLi/Mg) was 5688. In contrast, in the TBP/FeCl3 system with the same concentration, the ELi and βLi/Mg values were much lower at 74 % and 239, respectively. Furthermore, the TOP complex of Li+ had shorter Li − O bond lengths and a more negative binding energy, while that formed with Mg2+ had longer Mg − O bond lengths and the smallest HOMO–LUMO gap, indicating that TOP bonded more stably with Li+ and was less prone to Mg2+ extraction than TBP.

Engineering Small HOMO-LUMO Gaps in Polycyclic Aromatic Hydrocarbons with Topologically Protected States.

Topological phases in laterally confined low-dimensional nanographenes have emerged as versatile design tools that can imbue otherwise unremarkable materials with exotic band structures ranging from topological semiconductors and quantum dots to intrinsically metallic bands. The periodic boundary conditions that define the topology of a given lattice have thus far prevented the translation of this technology to the quasi-zero-dimensional (0D) domain of small molecular structures. Here, we describe the synthesis of a polycyclic aromatic hydrocarbon (PAH) featuring two localized zero modes (ZMs) formed by the topological junction interface between a trivial and nontrivial phase within a single molecule. First-principles density functional theory calculations predict a strong hybridization between adjacent ZMs that gives rise to an exceptionally small HOMO-LUMO gap. Scanning tunneling microscopy and spectroscopy corroborate the molecular structure of 9/7/9-double quantum dots and reveal an experimental quasiparticle gap of 0.16 eV, corresponding to a carbon-based small molecule long-wavelength infrared (LWIR) absorber.

Reply to the Comments on Planar Tetracoordinate Hydrogen: Pushing the Limit of Multicentre Bonding

AbstractRecently, Huo et al. has commented on our communication (Angew. Chem. Int. Ed. 2024, 63, e202317312, DOI: 10.1002/anie.202317312), regarding the multireference character (MRC) of our proposed cluster. Their argument is based on small HOMO–LUMO gap, fractional occupation density (FOD) and CASPT2(12,13) calculations. They also proposed that the singlet planar In4H+ cluster cannot be observed. We present our calculations which reveals that some of their arguments are based on wrong interpretation of data and inadequate use of methodology. While we certainly agree with the strong physical ground of FOD, CASSF and CASPT2 methodology, we believe that such analysis for clusters is not adequate.

Theoretical Photoelectron Spectroscopy of Quadruple-Bonded Dimolybdenum(II,II) and Ditungsten(II,II) Paddlewheel Complexes: Performance of Common Density Functional Theory Methods.

We have revisited the gas-phase photoelectron spectra of quadruple-bonded dimolybdenum(II,II) and ditungsten(II,II) paddlewheel complexes with modern density functional theory methods and obtained valuable calibration of four well-known exchange-correlation functionals, namely, BP86, OLYP, B3LYP*, and B3LYP. All four functionals were found to perform comparably, with discrepancies between calculated and experimental ionization potentials ranging from <0.1 to ∼0.5 eV, with the lowest errors observed for the classic pure functional BP86. All four functionals were found to reproduce differences in ionization potentials (IPs) between analogous Mo2 and W2 complexes, as well as large, experimentally observed ligand field effects on the IPs, with near-quantitative accuracy. The calculations help us interpret a number of differences between analogous Mo2 and W2 complexes through the lens of relativistic effects. Thus, relativity results in not only significantly lower IPs for the W2 complexes but also smaller HOMO-LUMO gaps and different triplet states relative to their Mo2 counterparts.

Ballistic Conductance through Porphyrin Nanoribbons.

The search for long molecular wires that can transport charge with maximum efficiency over many nanometers has driven molecular electronics since its inception. Single-molecule conductance normally decays with length and is typically far below the theoretical limit of G0 (77.5 μS). Here, we measure the conductances of a family of edge-fused porphyrin ribbons (lengths 1-7 nm) that display remarkable behavior. The low-bias conductance is high across the whole series. Charging the molecules in situ results in a dramatic realignment of the frontier orbitals, increasing the conductance to 1 G0 (corresponding to a current of 20 μA). This behavior is most pronounced in the longer molecules due to their smaller HOMO-LUMO gaps. The conductance-voltage traces frequently exhibit peaks at zero bias, showing that a molecular energy level is in resonance with the Fermi level. This work lays the foundations for long, perfectly transmissive, molecular wires with technological potential.

Screening novel candidates of ZL003-based organic dyes for dye-sensitized solar cells by modifying auxiliary electron acceptors: A theoretical study

In this work, a series of ZL003-based free-metal sensitizers with the donor-acceptor-π- conjugated spacer-acceptor (D-A-π-A) structure were designed by modifying auxiliary electron acceptors for the potential application in dye-sensitized solar cells. The energy levels of frontier molecular orbitals, absorption spectra, electronic transition, and photovoltaic parameters for all studied dyes were systematically evaluated using density functional theory (DFT)/time-dependent DFT calculations. Results illustrated that thienopyrazine (TPZ), selenadiazolopyridine (SDP), and thiadiazolopyridine (TDP) are excellent electron acceptors, and dye sensitizers functionalized by these acceptors have smaller HOMO-LUMO gaps, obviously red-shifted absorption bands and stronger light harvesting. The present study revealed that the photoelectric conversion efficiency (PCE) of ZL003 is around 13.42 % with a JSC of 20.21 mA·cm−2, VOC of 966 mV and FF of 0.688 under the AM 1.5G sun exposure, in good agreement with its experimental value (PCE = 13.6 ± 0.2 %, JSC = 20.73 ± 0.20 mA·cm−2, VOC = 956 ± 5 mV, and FF = 0.685 ± 0.005.). With the same procedure, the PCE values for M4, M6, and M7 were estimated to be as high as 19.93 %, 15.38 %, and 15.80 % respectively. Hence, these three dyes are expected to be highly efficient organic sensitizers applied in practical DSSCs.

Cyano disubstituted tetrabenzoindeno[2,1-a]fluorene: open-shell or closed-shell?

Organic diradicaloids have lately emerged as potential spintronic materials. We report the unprecedented synthesis of a near-IR absorbing indeno[2,1-a]fluorene derivative that displays remarkably low LUMO (-4.15 eV) and a small HOMO-LUMO gap (0.85 eV). NMR/EPR studies indicated its open-shell diradical property, which was supported by DFT calculations while suggesting a 30% diradical character and a small singlet (S)-triplet (T) gap (-2.52 kcal mol-1). A large bond length alternation of the as-indacene core for its single-crystals indicated a quinoidal contribution with greater antiaromaticity, which is in line with the small diradical character despite showing a small S-T gap.

Cyclopentene ring effects in cyanine dyes: a handle to fine-tune photophysical properties.

The aim of this study is to investigate the photophysical properties of a cyanine dye analogue by performing first-principles calculations based on density functional theory (DFT) and time dependent-DFT. Cationic cyanine dyes are the subject of great importance due to their versatile applications and the tunability of their photophysical properties, such as by modifying their end groups and chain length. An example of this is the vinylene shift, which is experimentally known for these molecules, and it consists of a bathochromic (red) shift of approximately 100 nm of the 0-0 vibronic transition when a vinyl group is added to the polymethine chain. Our study shows that when the saturated moiety C2H4 of the cyclopentene ring is added to the chain, it interacts with the conjugated π-system, resulting in a smaller HOMO-LUMO gap. Here, we demonstrate the origin of this interaction and how it can be used to fine tune the absorption energies of this class of dyes.

Twisted diphenoquinones fused with thiophene rings: thiophene analogs of bianthrone.

The twisted conformer of bistricyclic aromatic enes (BAEs) has a small HOMO-LUMO gap owing to the twisted double bond. In this study, we synthesized diphenoquinones fused with thiophene rings as a new twisted conformer-predominant BAE. They exhibited deep LUMO energy levels and apparent n-type semiconductor properties.

Insight into the influence of environmental factors on selenite removal from desulfurization wastewater by NZVI@AC: An experimental and theoretical study

Nano zero-valent iron (NZVI) technology has shown good potential for the treatment of selenium in wastewater. In this study, NZVI was loaded on activated carbon (AC) by carbothermal reduction method to synthesize high-efficiency adsorbent (NZVI@AC). The agglomeration of NZVI was suppressed and its reactivity was improved. The optimum preparation temperature of NZVI@AC (600 °C) was determined by comparing its purity. Moreover, the synergistic effect between the active component (NZVI) and the support (AC) was investigated on the basis of the density functional theory method. The smaller HOMO-LUMO gap (0.87 eV) and charge distribution of NZVI@AC indicated favorable electron transfer and enhanced chemical reactivity. The adsorption and reduction to Se(0)/Se(-II) were elucidated as the underlying mechanisms for the removal of selenite by comparative analysis of the morphological transformation of iron and selenium species. Furthermore, the selenite removal performance of NZVI@AC was investigated on account of the impact of dissolved oxygen and pH values, and the interaction mechanism of these factors was revealed. The decrease of solution pH and dissolved oxygen concentration are effective ways to improve the removal efficiency of selenite.

Size- and Voltage-Dependent Electron Transport of C2N-Rings-Based Molecular Chains.

C2N-ring-based molecular chains were designed at the molecular level and theoretically demonstrated to show distinctive and valuable electron transport properties that were superior to the parent carbonaceous system and other similar nanoribbon-based molecular chains. This new -type molecular chain presented an exponential attenuation of the conductance and electron transmission with the length. Essentially, the molecular chain retained the electron-resonant tunneling within 7 nm and the dominant transport orbital was the LUMO. Shorter molecular chains with stronger conductance anomalously possessed a larger tunnel barrier energy, attributing to the compensation of a much smaller HOMO-LUMO gap, and these two internal factors codetermined the transport capacity. Some influencing factors were also studied. In contrast to the common O impurity with a tiny effect on electron transmission of the C2N rings chain, the common H impurity clearly improved it. When the temperature was less than 400 K, the electron transmission varied with temperature within a narrow range, and the structural disorder deriving from proper heating did not greatly modify the transmission possibility and the exponentially decreasing tendency with the length. In a non-equilibrium condition, the current increased overall with the bias but the growth rate varied with size. A valuable negative differential resistance (NDR) effect appeared in longer molecular chains with an even number of big carbon-nitrogen rings and strengthened with size. The emergence of such an effect originated from the reduction in transmission peaks. The conductance of longer molecular chains was enhanced with the voltage but the two shortest ones presented completely different trends. Applying the bias was demonstrated to be an effective way for C2N-ring-based molecular chains to slow down the conductance decay constant and affect the transport regime. C2N-ring-based molecular chains show a perfect application in tunneling diodes and controllable molecular devices.