Tuning polymer-backbone coplanarity and conformational order to achieve high-performance printed all-polymer solar cells.

All-polymer solar cells (all-PSCs) offer improved morphological and mechanical stability compared with those containing small-molecule-acceptors (SMAs). They can be processed with a broader range of conditions, making them desirable for printing techniques. In this study, we report a high-performance polymer acceptor design based on bithiazole linker (PY-BTz) that are on par with SMAs. We demonstrate that bithiazole induces a more coplanar and ordered conformation compared to bithiophene due to the synergistic effect of non-covalent backbone planarization and reduced steric encumbrances. As a result, PY-BTz shows a significantly higher efficiency of 16.4% in comparison to the polymer acceptors based on commonly used thiophene-based linkers (i.e., PY-2T, 9.8%). Detailed analyses reveal that this improvement is associated with enhanced conjugation along the backbone and closer interchain π-stacking, resulting in higher charge mobilities, suppressed charge recombination, and reduced energetic disorder. Remarkably, an efficiency of 14.7% is realized for all-PSCs that are solution-sheared in ambient conditions, which is among the highest for devices prepared under conditions relevant to scalable printing techniques. This work uncovers a strategy for promoting backbone conjugation and planarization in emerging polymer acceptors that can lead to superior all-PSCs.

Monomeric gold hydrides for carbon dioxide reduction: ligand effect on the reactivity.

We analyzed the ligand electronic effect in the reaction between a [LAu(I)H]0/- hydride species and CO2, leading to a coordinated formate [LAu(HCOO)]0/-. We explored 20 different ligands, such as carbenes, phosphines and others, carefully selected to cover a wide range of electron-donor and -acceptor properties. We included in the study the only ligand, an NHC-coordinated diphosphene, that, thus far, experimentally demonstrated facile and reversible reaction between the monomeric gold(I) hydride and carbon dioxide. We elucidated the previously unknown reaction mechanism, which resulted to be concerted and common to all the ligands: the gold-hydrogen bond attacks the carbon atom of CO2 with one oxygen atom coordinating to the gold center. A correlation between the ligand σ donor ability, which affects the electron density at the reactive site, and the kinetic activation barriers of the reaction has been found. This systematic study offers useful guidelines for the rational design of new ligands for this reaction, while suggesting a few promising and experimentally accessible potential candidates for the stoichiometric or catalytic CO2 activation.

Elucidating the Electronic Nature of Rh-based Paddlewheel Catalysts from 103 Rh NMR Chemical Shifts: Insights from Quantum Mechanical Calculations.

The tremendous importance of dirhodium paddlewheel complexes for asymmetric catalysis is largely the result of an empirical optimization of the chiral ligand sphere about the bimetallic core. It was only recently that a H(C)Rh triple resonance 103 Rh NMR experiment provided the long-awaited opportunity to examine - with previously inconceivable accuracy - how variation of the ligands impacts on the electronic structure of such catalysts. The recorded effects are dramatic: formal replacement of only one out of eight O-atoms surrounding the metal centers in a dirhodium tetracarboxylate by an N-atom results in a shielding of the corresponding Rh-site of no less than 1000 ppm. The current paper provides the theoretical framework that allows this and related experimental observations made with a set of 19 representative rhodium complexes to be interpreted. In line with symmetry considerations, it is shown that the shielding tensor responds only to the donor ability of the equatorial ligands along the perpendicular principal axis. Axial ligands, in contrast, have no direct effect on shielding but may come into play via the electronic c i s ${cis}$ -effect that they exert onto the neighboring equatorial sites. On top of these fundamental interactions, charge redistribution within the core as well as the electronic t r a n s ${trans}$ -effect of ligands of different donor strengths is reflected in the recorded 103 Rh NMR shifts.

Cooperative small molecule activation by apolar and weakly polar bonds through the lens of a suitable computational protocol.

Small molecule activation processes are central in chemical research and cooperativity is a valuable tool for the fine-tuning of the efficiency of these reactions. In this contribution, we discuss recent and remarkable examples in which activation processes are mediated by bimetallic compounds featuring apolar or weakly polar metal-metal bonds. Relevant experimental breakthroughs are thoroughly analyzed from a computational perspective. We highlight how the rational and non-trivial application of selected computational approaches not only allows rationalization of the observed reactivities but also inferring of general principles applicable to activation processes, such as the breakdown of the structure-reactivity relationship in carbon dioxide activation in a cooperative framework. We finally provide a simple yet unbiased computational protocol to study these reactions, which can support experimental advances aimed at expanding the range of applications of apolar and weakly polar bonds as catalysts for small molecule activation.

Radical-like reactivity for dihydrogen activation by coinage metal-aluminyl complexes: computational evidence inspired by experimental main group chemistry.

The computational study of an unprecedented reactivity of coinage metal-aluminyl complexes with dihydrogen is reported. In close resemblance to group 14 dimetallenes and dimetallynes, the complexes are predicted to activate H2 under mild conditions. Two different reaction pathways are found disclosing a common driving force, i.e., the nucleophilic behavior of the electron-sharing M-Al (M = Cu, Ag, Au) bond, which enables a cooperative and diradical-like mechanism. This mode of chemical reactivity emerges as a new paradigm for dihydrogen activation and calls for experimental feedback.

Widening the Landscape of Small Molecule Activation with Gold-Aluminyl Complexes: A Systematic Study of E-H (E=O, N) Bonds, SO2 and N2 O Activation.

The electronic features of gold-aluminyl complexes have been thoroughly explored. Their similarity with Group 14 dimetallenes and other metal-aluminyl complexes suggests that their reactivity with small molecules beyond carbon dioxide could be accessed. In this work, the reactivity of the [t Bu3 PAuAl(NON)] (NON=4,5-bis(2,6 diisopropylanilido)-2,7-ditert-butyl-9,9-dimethylxanthene) complex towards water, ammonia, sulfur dioxide and nitrous oxide is computationally explored. The reaction mechanisms computed for each substrate strongly suggest that all activation processes are in principle experimentally feasible. Electronic structure analysis highlights that, in all cases, the reactivity is driven by the presence of the poorly polarized electron-sharing gold-aluminyl bond, which induces a radical-like reactivity of the complex towards all the substrates. A flat topology of the potential energy surface (PES) has been found for the reaction with N2 O, where two almost isoenergetic transition states can be located along the same reaction coordinate with different geometries, suggesting that the N2 O binding mode may not be a good indicator of the nature of N2 O activation in a cooperative bimetallic reactivity. In addition, the catalytic potentialities of these complexes have been explored in the framework of nitrous oxide reduction. The study reveals that the [t Bu3 PAuAl(NON)] complex might be an efficient catalyst towards oxidation of phosphines (and boranes) via N2 O reduction. These findings underline recurring trends in the novel chemistry of gold-aluminyl complexes and call for experimental feedbacks.

Mechanistic Study of Alkyne Insertion into Cu-Al and Au-Al Bonds: A Paradigm Shift for Coinage Metal Chemistry.

In this work, the mechanism of the insertion reaction of 3-hexyne into Cu-Al and Au-Al bonds in M-aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu-Al and Au-Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold-aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu-Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site─usually showing higher efficiency than copper as a "standard" electrophile in alkyne activation─arises from a common feature, i.e., the highly stable 6s Au orbital. The relativistic lowering of the 6s orbital, making it more suitable for accepting electron density and thus enhancing the electrophilicity of gold complexes, in the gold-aluminyl system is responsible for a less nucleophilic Au-Al bond and, consequently, a less efficient alkyne insertion. These findings demonstrate that the unconventional electronic structure and the electron-sharing nature of the M-Al bond induce a paradigm shift in the properties of coinage metal complexes. In particular, the peculiar radical-like reactivity, previously shown also with carbon dioxide, suggests that these complexes might efficiently insert/activate other small molecules, opening new and unexplored paths for their reactivity.

Frozen-Density Embedding for Including Environmental Effects in the Dirac-Kohn-Sham Theory: An Implementation Based on Density Fitting and Prototyping Techniques.

Frozen density embedding (FDE) represents an embedding scheme in which environmental effects are included from first-principles calculations by considering the surrounding system explicitly by means of its electron density. In the present paper, we extend the full four-component relativistic Dirac-Kohn-Sham (DKS) method, as implemented in the BERTHA code, to include environmental and confinement effects with the FDE scheme (DKS-in-DFT FDE). The implementation, based on the auxiliary density fitting techniques, has been enormously facilitated by BERTHA's python API (PyBERTHA), which facilitates the interoperability with other FDE implementations available through the PyADF framework. The accuracy and numerical stability of this new implementation, also using different auxiliary fitting basis sets, has been demonstrated on the simple NH3-H2O system, in comparison with a reference nonrelativistic implementation. The computational performance has been evaluated on a series of gold clusters (Aun, with n = 2, 4, 8) embedded into an increasing number of water molecules (5, 10, 20, 40, and 80 water molecules). We found that the procedure scales approximately linearly both with the size of the frozen surrounding environment (consistent with the underpinnings of the FDE approach) and with the size of the active system (in line with the use of density fitting). Finally, we applied the code to a series of heavy (Rn) and super-heavy elements (Cn, Fl, Og) embedded in a C60 cage to explore the confinement effect induced by C60 on their electronic structure. We compare the results from our simulations, with respect to more-approximate models employed in the atomic physics literature. Our results indicate that the specific interactions described by FDE are able to improve upon the cruder approximations currently employed, and, thus, they provide a basis from which to generate more-realistic radial potentials for confined atoms.

How reduced are nucleophilic gold complexes?

Nucleophilic formal gold(-I) and gold(I) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations. The results indicate gold(0) centres engaging in electron-sharing bonding with Al- and B- based ligands. Multiconfigurational (CASSCF) calculations corroborate the findings, highlighting the gap between the electonic structures and the oxidation state formalism.

Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide.

The electronic properties of aluminyl anions have been reported to be strictly related to those of carbenes, which are well-known to be easily tunable via selected structural modifications imposed on their backbone. Since peculiar reactivity of gold-aluminyl complexes towards carbon dioxide has been reported, leading to insertion of CO2 into the Au-Al bond, in this work the electronic structure and reactivity of Au-Al complexes with different aluminyl scaffolds have been systematically studied and compared to carbene analogues. The analyses reveal that, instead, aluminyls and carbenes display a very different behavior when bound to gold, with the aluminyls forming an electron-sharing and weakly polarized Au-Al bond, which turns out to be poorly modulated by structural modifications of the ligand. The reactivity of gold-aluminyl complexes towards CO2 shows, both qualitatively and quantitatively, similar reaction mechanisms, reflecting the scarce tunability of their electronic structure and bond nature. This work provides further insights and perspectives on the properties of the aluminyl anions and their behavior as coordination ligands.

Gold-Aluminyl and Gold-Diarylboryl Complexes: Bonding and Reactivity with Carbon Dioxide.

The unconventional carbon dioxide insertion reaction of a gold-aluminyl [tBu3PAuAl(NON)] complex has been recently shown to be related to the electron-sharing character of the Au-Al bond that acts as a nucleophile and stabilizes the insertion product through a radical-like behavior. Since a gold-diarylboryl [IPrAuB(o-tol)2] complex with similar reactivity features has been recently reported, in this work we computationally investigate the reaction of carbon dioxide with [LAuX] (L = phosphine, N-heterocyclic carbene (NHC); X = Al(NON), B(o-tol)2) complexes to get insights into the Al/B anionic and gold ancillary ligand effects on the Au-Al/B bond nature, electronic structure, and reactivity of these compounds. We demonstrate that the Au-Al and Au-B bonds possess a similar electron-sharing nature, with diarylboryl complexes displaying a slightly more polarized bond as Au(δ+)-B(δ-). This feature reduces the radical-like reactivity toward CO2, and the Al/B anionic ligand effect is found to favor aluminyls over boryls, despite the greater oxophilicity of B. Remarkably, the ancillary ligand of gold has a negligible electronic trans effect on the Au-X bond and only a minor impact on the formation of the insertion product, which is slightly more stable with carbene ligands. Surprisingly, we find that the modification of the steric hindrance at the carbene site may exert a sizable control over the reaction, with more sterically hindered ligands thermodynamically disfavoring the formation of the CO2 insertion product.

An ETS-NOCV-based computational strategies for the characterization of concerted transition states involving CO2.

Due to the presence of both a slightly acidic carbon and a slightly basic oxygen, carbon dioxide is often involved in concerted transition states (TSs) with two (or more) different molecular events interlaced in the same step. The possibility of isolating and quantitatively evaluating each molecular event would be important to characterize and understand the reaction mechanism in depth. This could be done, in principle, by measuring the relevant distances in the optimized TS, but often distances are not accurate enough, especially in the presence of many simultaneous processes. Here, we have applied the Extended Transition State-Natural Orbital for Chemical Valence-method (ETS-NOCV), also in combination with the Activation Strain Model (ASM) and Energy Decomposition Analysis (EDA), to separate and quantify these molecular events at the TS of both organometallic and organic reactions. For the former, we chose the decomposition of formic acid to CO2 by an iridium catalyst, and for the latter, a CO2 -mediated transamidation and its chemical variations (hydro- and aminolysis of an ester) as case studies. We demonstrate that the one-to-one mapping between the "molecular events" and the ETS-NOCV components is maintained along the entire lowest energy path connecting reactants and products around the TS, thus enabling a detailed picture on the relative importance of each interacting component. The methodology proposed here provides valuable insights into the effect of different chemical substituents on the reaction mechanism and promises to be generally applicable for any concerted TSs.

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold-Aluminyl, -Gallyl, and -Indyl Complexes.

Anionic aluminum(I) anions ("aluminyls") are the most recent discovery along Group 13 anions, and the understanding of the unconventional reactivity they are able to induce at a coordinated metal site is at an early stage. A striking example is the efficient insertion of carbon dioxide into the Au-Al bond of a gold-aluminyl complex. The reaction occurs via a cooperative mechanism, with the gold-aluminum bond being the actual nucleophile and the Al site also behaving as an electrophile. In the complex, the Au-Al bond has been shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2. In this work, the analogous reactivity with isostructural Au-X complexes (X = Al, Ga, and In) is computationally explored. We demonstrate that a kinetically and thermodynamically favorable reactivity with CO2 may only be expected for the gold-aluminyl complex. The Au-Al bond nature, which features the most (nonpolar) electron-sharing character among the Group 13 anions analyzed here, is responsible for its highest efficiency. The radical-like reactivity appears to be a key ingredient to stabilize the CO2 insertion product. This investigation elucidates the special role of Al in these hetero-binuclear compounds, providing new insights into the peculiar electronic structure of aluminyls, which may help for the rational control of their unprecedented reactivity toward carbon dioxide.

Reactivity of a Gold-Aluminyl Complex with Carbon Dioxide: A Nucleophilic Gold?

A gold-aluminyl complex has been recently reported to feature an unconventional gold nucleophilic center, which was revealed through reactivity with carbon dioxide leading to the Au-CO2 coordination mode. In this work, we computationally investigate the reaction mechanism, which is found to be cooperative, with the gold-aluminum bond being the actual nucleophile and Al also behaving as electrophile. The Au-Al bond is shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO2.

The mechanism of the gold(I)-catalyzed Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-ol via 4-endo-dig cyclization.

With the aim of rationalizing the experimental counterion- and solvent-dependent reactivity in the gold(i)-catalyzed Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-ol, a computational mechanistic study unraveled the unexpected formation of a gold-oxetene intermediate via commonly unfavorable 4-endo-dig cyclization triggered by the counterion in low polarity solvents.

Spectroscopic/Bond Property Relationship in Group 11 Dihydrides via Relativistic Four-Component Methods.

Group 11 dihydrides MH2- (M = Cu, Ag, Au, Rg) have been much less studied than the corresponding MH compounds, despite having potentially several interesting applications in chemical research. In this work, their main spectroscopic constants (bond lengths, dissociation energies, and force constants) have been evaluated by means of highly accurate relativistic four-component coupled cluster (4c-CCSD(T)) calculations in combination with large basis sets. Periodic trends have been quantitatively explained by the charge-displacement/natural orbitals for chemical valence (CD-NOCV) analysis based on the four-component relativistic Dirac-Kohn-Sham method, which allows a consistent picture of the nature of the M-H bond to be obtained on going down the periodic table in terms of Dewar-Chatt-Duncanson bonding components. A strong ligand-to-metal donation drives the M-H bond and it is responsible for the heterolytic (HM···H-) dissociation energies to increase monotonically from Cu to Rg, with RgH2- showing the strongest and most covalent M-H bond. The "V"-shaped trend observed for the bond lengths, dissociation energies, and stretching frequencies can be explained in terms of relativistic effects and, in particular, of the relativistically enhanced sd hybridization occurring at the metal, which affects the metal-ligand distances in heavy transition-metal complexes. The sd hybridization is very small for Cu and Ag, whereas it becomes increasingly important for Au and Rg, being responsible for the increasing covalent character of the bond, the sizable contraction of the Au-H and Rg-H bonds, and the observed trend. This work rationalizes the spectroscopic/bond property relationship in group 11 dihydrides within highly accurate relativistic quantum chemistry methods, paving the way for their applications in chemical bond investigations involving heavy and superheavy elements.

Ground and excited electronic states of AuH2via detachment energies on AuH2- using state-of-the-art relativistic calculations.

Photoelectron spectroscopy (PES) is a well-known technique which provides unique information about the electronic structure of anionic and neutral species of simple molecules containing heavy elements; however, the detailed interpretation of the resulting experimental spectra can be very complex and theoretical support is mandatory. In this work, based on the available vibrationally resolved PES experiments for gold dihydride (Liu, H.-T. et al., Chem. Sci., 2012, 3, 3286), we have employed several relativistic theoretical approaches with the aim of reproducing experimental photoelectron Detachment Energies (DEs) of AuH2- to give a neutral open-shell molecule, AuH2. The results are discussed in terms of relativistic effects, orbital relaxation and electron correlation. In order to reproduce accurate DEs it has been necessary to include all these effects in a consistent manner at a high degree of accuracy, by means of the equation-of-motion coupled-cluster theory (EOM-IP-CCSD) based on the relativistic exact two-component Hamiltonian (Shee A. et al. J. Chem. Phys., 2018, 174113). This method has also been applied for investigating the ground and low-lying electronic potential energy surfaces of the neutral open shell AuH2 species. The equilibrium geometry of the AuH2 ground state is found to be bent, which is fully consistent with the experimental findings, while all the excited states, including the first, which was previously suggested to have a slightly bent structure, are found to be linear. In the linear centrosymmetric nuclear configuration (which corresponds to the equilibrium geometry of the anion, AuH2-), we find that the first excited state and ground state are very close in energy and the ground state is characterized by an unexpected symmetry breaking in the direction of the asymmetric stretching, due to the pseudo-Jahn-Teller effect. This effect depends on the energy difference between these two electronic states and disappears when the spin-orbit coupling is neglected. The picture that emerges here is intriguing and demonstrates that the interpretation, for which the vibronic transitions that were previously assigned to a slightly bent structure of the first excited state needs to be revised and that a full rationalization of the PES spectra would require the explicit inclusion of the nuclear dynamical effects, beyond the Born-Oppenheimer (BO) approximation. From a methodological point of view, the relativistic EOM-IP-CCSD method results are highly accurate and capable of giving a well-balanced description of the anionic and neutral species, which is a key aspect for the interpretation of the PES spectra in open-shell heavy element compounds.

Spin-orbit coupling is the key to unraveling intriguing features of the halogen bond involving astatine.

The effect of spin-orbit coupling (SOC) on the halogen bond involving astatine has been investigated using state-of-the-art two- and four-component relativistic calculations. Adducts between Cl-X (X = Cl, Br, I and At) and ammonia have been selected to establish a trend on going down the periodic table. The SOC influence has been explored not only on the geometric and energetic features that can be used to characterize the halogen bond strength but also on the three main contributions to it that are the charge transfer, the "σ-hole" (i.e. the localized region with a net positive electrostatic potential at the halogen site) and the "polar flattening" (which is related to the effective shape of the halogen site). A surprisingly large increase of the Cl-At dipole moment, due to the inclusion of SOC, has been worked out using four-component CCSD(T) reference calculations, indicating that this bond is significantly more ionic than one may predict. Due to the SOC effect, which induces a peculiar charge accumulation on the At side in the Cl-At dimer, a weakening of the astatine-mediated halogen bond occurs arising from the (i) reduced amount of charge transfer, (ii) decrease of the polar flattening and (iii) lowering of the short-range Coulomb potential. The analysis of the electronic structure of the Cl-At moiety allows for a rationalization of the SOC effects on all the considered features of the halogen bond, including an unprecedented unsymmetrical charge back-donation from Cl-At to ammonia.

Cationic Gold(I) Diarylallenylidene Complexes: Bonding Features and Ligand Effects.

Using computational approaches, we qualitatively and quantitatively assess the bonding components of a series of experimentally characterized Au(I) diarylallenylidene complexes (N.Kim, R.A.Widenhoefer, Angew. Chem. Int. Ed. 2018, 57, 4722-4726). Our results clearly demonstrate that Au(I) engages only weakly in π-backbonding, which is, however, a tunable bonding component. Computationally identified trends in bonding are clearly correlated with the substitution patterns of the aryl substituents in the Au(I) diarylallenylidene complexes and good agreement is found with the previously reported experimental data, such as IR spectra, 13 C NMR chemical shifts and rates of decomposition together with their corresponding barrier heights, further substantiating the computational findings. The description of the bonding patterns in these complexes allow predictions of their spectroscopic features, their reactivity and stability.

Alkyne Activation with Gold(III) Complexes: A Quantitative Assessment of the Ligand Effect by Charge-Displacement Analysis.

A quantitative assessment of the Dewar-Chatt-Duncanson components of the Au(III)-alkyne bond in a series of cationic and dicationic bis- and monocyclometalated gold(III) complexes with 2-butyne via charge-displacement (CD) analysis is reported. Bonding between Au(III) and 2-butyne invariably shows a dominant σ donation component, a smaller, but significant, π back-donation, and a remarkable polarization of the alkyne CC triple bond toward the metal fragment. A very large net electron charge transfer from CC triple bond to the metal fragment results, which turns out to be unexpectedly insensitive to the charge of the complex and more strictly related to the nature of the ancillary ligand. The combination of σ donation, π back-donation, and polarization effects is in fact modulated by the different ligand frameworks, with ligands bearing atoms different from carbon in trans position with respect to the alkyne emerging as especially interesting for both imparting Au(III)-alkyne bond stability and inducing a more effective alkyne activation. A first attempt to figure out a rationale on the bonding/reactivity relationship for Au(III)-alkyne is made by performing a comparative study in a model nucleophilic attack of water to the alkyne triple bond. Smaller π back-donation facilitates alkyne slippage in the transition states, which is energetically less demanding for Au(III) than for Au(I), and suggests a greater propensity of Au(III) to facilitate the nucleophilic attack.