Molecular models of PM6 for non-fullerene acceptor organic solar cells: How DAD and ADA structures impact charge separation and charge recombination.

The quadrupole moment of a non-fullerene acceptor (NFA) generated by the constituent electron donor (D) and acceptor (A) units is a significant factor that affects the charge separation (CS) and charge recombination (CR) processes in organic photovoltaics (OPVs). However, its impact on p-type polymer domains remains unclear. In this study, we synthesized p-type molecules, namely acceptor-donor-acceptor (ADA) and donor-acceptor-donor (DAD), which are components of the benchmark PM6 polymer (D: benzodithiophene and A: dioxobenzodithiophene).

Epoxide/CO Cycloaddition Reaction Catalyzed by Indium Chloride Complexes Supported by Constrained Inden Schiff-Base Ligands.

Cyclic carbonates have received significant interests for uses as reagents, solvents, and monomers. The coupling reaction of epoxides with carbon dioxide (CO ) to produce cyclic carbonate is an attractive route which can significantly reduce greenhouse gas emissions and environmental hazards. Herein, a series of five indium chloride complexes supported by inden Schiff-base ligands were reported along with four X-ray crystal structures.

Ring-Opening Co- and Terpolymerization of Epoxides, Cyclic Anhydrides, and l-Lactide Using Constrained Aluminum Inden Complexes.

Seven constrained aluminum inden complexes having different substituents and diamine backbones were developed for the ring-opening copolymerization (ROCOP) of epoxides and bulky cyclic anhydrides giving alternating polyesters with ranging from 49 to 226 °C. Among several catalyst/cocatalyst screenings, the aluminum inden complex having a rigid phenylene backbone coupled with 4-dimethylaminopyridine showed the best performance giving linear polyesters. In the case of cyclohexene oxide (CHO) and succinic anhydride (SA), the linear poly(CHO--SA) could be transformed to cyclic polymer when the polymerization was left under prolonged reaction time to induce intramolecular transesterification.

Enhancement of Ethylene and Ethylene/1-Hexene (Co)polymerization Activities by Titanium(IV) and Zirconium(IV) Complexes Bearing Constrained Hydroxyindanone-Imine Ligands.

A new series of catalysts for ethylene and ethylene/1-hexene (co)polymerizations bearing constrained hydroxyindanone-imine ligands was developed for titanium(IV) and zirconium(IV) metals with variations of steric and electronic contributions on the ligands. X-ray crystal structures revealed significantly higher open space for the constrained titanium and zirconium complexes, compared to the conventional FI counterparts. Upon activation with MAO, significantly higher ethylene polymerization activities (up to 379.

Antioxidant and Anticancer Potential of Bioactive Compounds from Cell Suspension Culture.

The potential benefits of natural plant extracts have received attention in recent years, encouraging the development of natural products that effectively treat various diseases. This is the first report on establishing callus and cell suspension cultures of (L.) Kurz.

Complexity of imine and amine Schiff-base tin(II) complexes: drastic differences of amino and pyridyl side arms.

A series of homoleptic and heteroleptic imine and amine Schiff-base tin(II) complexes containing dimethylamino and pyridyl side arms were synthesized and structurally characterized. While the tin complexes containing the dimethylamino side arm could be prepared in good yield, unusual cyclodimerization and ligand dimerization were observed for the first time for Schiff-base tin complexes having a pyridyl side arm due to the added stabilization offered by the pyridyl ring. The amine Schiff-base tin(II) complexes were active for the ring-opening copolymerization of succinic anhydride (SA) and cyclohexene oxide (CHO) at 110 °C giving highly alternating poly(SA--CHO).

Highly Active Homoleptic Zinc and Magnesium Complexes Supported by Constrained Reduced Schiff Base Ligands for the Ring-Opening Polymerization of Lactide.

New homoleptic zinc and magnesium complexes containing constrained reduced Schiff base ligands based on substituted 7-hydroxy-1-indanone were successfully synthesized and used as a catalyst for the polymerization of lactide. The ligands contain a side arm having different basicity because dimethylamino, pyridyl, and furfuryl groups are shown to greatly affect the polymerization rates. The homoleptic zinc complex containing constrained reduced Schiff base ligands and a dimethylamino side arm was highly active, giving a 92% conversion of l-lactide in 3 min using [LA]:[Zn]:[BnOH] = 500:1:2 at room temperature.

Bifunctional zinc and magnesium Schiff-base complexes containing quaternary ammonium side-arms for epoxide/CO coupling reactions.

Novel bifunctional zinc and magnesium Schiff-base complexes containing quaternary ammonium halide side-arms were developed. Zinc complex 1Et-I (0.02 mol%) having an iodide anion has shown the highest TOF for the propylene oxide/CO coupling reaction of up to 459 h.

Cycloaddition of carbon dioxide to epoxides by highly active constrained aluminum chloride complexes.

The transformation of carbon dioxide (CO) and epoxides to cyclic carbonates has gained much interest due to its low cost, abundance, low toxicity, and renewability. Therefore, novel constrained aluminum chloride complexes were developed based on bis(salicylimine) ligands for epoxides/CO coupling reactions. The five-membered rings attached to the aromatic rings were designed to enlarge the coordination pocket around the aluminum center as demonstrated by single-crystal X-ray crystallography.

Highly Active Chromium Complexes Supported by Constrained Schiff-Base Ligands for Cycloaddition of Carbon Dioxide to Epoxides.

Novel constrained Schiff-base ligands (inden) were developed based on the well-known salen ligands. Chromium complexes supported by the constrained inden ligands were successfully synthesized and used as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO). The catalyst having -butyl (Bu) groups as substituents in combination with tetrabutylammonium bromide (TBAB) as a cocatalyst exhibited very high catalytic activity with a turnover frequency of up to 14800 h for the conversion of CO and propylene oxide into propylene carbonate exclusively at 100 °C and 300 psi of CO under solvent-free conditions.

Comparative bindings of lactones, lactide, and cyclic carbonates: experimental insights into the coordination step of polymerization.

Comparative bindings of several renowned monomers were investigated experimentally using B(CF) as a Lewis acid model for the coordination step in ring-opening polymerization. A complete series of the X-ray crystal structures of the B(CF) adducts with the monomers was reported. The X-ray structural studies and spectroscopic data revealed a coordination strength in the order lactones > tetrahydrofuran > cyclic carbonates > lactide.

Ring-Opening Copolymerizaton of Cyclohexene Oxide and Succinic Anhydride by Zinc and Magnesium Schiff-Base Complexes Containing Alkoxy Side Arms.

The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a promising method for the synthesis of new polyesters with various polymer properties. Among previously reported metal catalysts for ROCOP, the Schiff-base complexes have gained significant attention because of their ease of synthesis and modification. In this work, zinc and magnesium complexes containing Schiff-base ligands with different alkoxy side arms [-(CH)O- and -(CH)O-] were synthesized and shown to have a cubane metal core by X-ray crystal structures.

Synthesis and characterization of guanidinate tin(ii) complexes for ring-opening polymerization of cyclic esters.

Novel homoleptic and heteroleptic (guanidinate)tin(ii) complexes were successfully synthesized and structurally characterized. The first heteroleptic (guanidinato)tin(ii) alkoxide complex was synthesized but found to be unstable leading to the corresponding bis(guanidinate)tin(ii) complex. The catalytic activities of bis(guanidinate)tin(ii) complexes having different substituents at the nitrogen atoms (isopropyl (1), cyclohexyl (2), and p-tolyl (3)) were investigated in the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and lactide (LA).

Influence of catalyst nuclearity on copper-catalyzed aerobic alcohol oxidation.

Reactions of CuX with the bis(triazolyl) ligand Hbtm [bis(1-benzyl-1H-1,2,3-triazol-4-yl)phenylmethanol] in CH2Cl2 afforded trinuclear copper(ii) complexes with a core structure (μ-X)Cu3(μ-κ3-N,O,N-btm)3(L)2+ [X = Cl, L = CH3OH (1); X = Br, L = H2O (2)], while a similar reaction of [Cu(CH3CN)4](PF6) with the mono(triazolyl) ligand HPhtm [(1-benzyl-1H-1,2,3-triazol-4-yl)diphenylmethanol] resulted in the mononuclear complex [Cu(κ2-N,O-Phtm)(κ2-N,O-HPhtm)(κ1-N-HPhtm)][PF6] (3). The structural characterization of these complexes was made by single-crystal X-ray crystallography in combination with elemental and ESI mass analyses. Catalytic studies toward aerobic oxidation of benzyl alcohol to benzaldehyde revealed that the trinuclear 1 and 2 exhibited higher activities than the mononuclear 3 in both CH3CN and EtOH/H2O solvent systems.

Highly efficient metal(iii) porphyrin and salen complexes for the polymerization of rac-lactide under ambient conditions.

Ligated metal(iii) complexes, Al(iii), In(iii), Cr(iii), and Co(iii), containing tetraphenylporphyrin (TPP) and cyclohexylsalen (Cy-salen) ligands were investigated for the polymerization of rac-lactide (rac-LA). A combination of metal complexes, co-catalyst, and co-initiator was shown to be highly efficient for the ring-opening polymerization of rac-LA at room temperature. Influences of metal centers, ligands, and co-catalysts were investigated.

Polymerization of ε-Caprolactone Using Bis(phenoxy)-amine Aluminum Complex: Deactivation by Lactide.

Polymerizations of biodegradable lactide and lactones have been the subjects of intense research during the past decade. They can be polymerized/copolymerized effectively by several catalyst systems. With bis(phenolate)-amine aluminum complex, we have shown for the first time that lactide monomer can deactivate the aluminum complex during the ongoing polymerization of ε-caprolactone to a complete stop.

Hierarchical FAU/ZIF-8 Hybrid Materials as Highly Efficient Acid-Base Catalysts for Aldol Condensation.

The composite of hierarchical faujasite nanosheets and zeolitic imidazolate framework-8 (Hie-FAU-ZIF-8) has been successfully prepared via a stepwise deposition of ZIF-8 on modified zeolite surfaces. Compared to the direct deposition of metal organic frameworks (MOFs) on zeolite surfaces, ZIF-8 nanospheres were selectively attached to the external surfaces of the MOF ligand-grafted FAU crystals because of the enhancing interaction between the zeolite and MOF in the composite. In addition, the degree of surface functionalization can be greatly enhanced because of the presence of hierarchical structures.

Synthesis of cyclic polyesters: effects of alkoxy side chains in salicylaldiminato tin(II) complexes.

A new class of salicylaldiminato tin(II) catalysts having different alkoxy side chains has been developed. The ligands were modified to have different lengths and flexibilities such as –(CH2)2– (2a), –(CH2)3– (2b), –(ortho-C6H4)CH2– (2c) and –(CH2)2–O–(CH2)2– (2d). Complexes 2a, b were characterized crystallographically revealing a more constrained environment around the metal in complex 2a.

Ethylene polymerisation and ethylene/norbornene copolymerisation by using aryloxo-modified vanadium(V) complexes containing 2,6-difluoro-, dichloro-phenylimido complexes.

Aryloxo-modified vanadium(V) dichloride complexes containing a dichloro- or difluoro-phenylimido ligand of the type, V(N-2,6-X2C6H3)Cl2(O-2,6-R2C6H3) [X = Cl (1), F (2); R = Me (a), F (b)], showed remarkable catalytic activity in ethylene polymerisation and the copolymerisation with norbornene (NBE) in the presence of Et2AlCl; the activities were higher than that of V(N-2,6-Me2C6H3)Cl2(O-2,6-Me2C6H3) reported previously. Complex 1a is a suitable catalyst precursor in terms of not only the activity, but also synthesis of high molecular weight copolymers with both unimodal molecular weight distributions and uniform compositions.

Syntheses of bis(pyrrolylaldiminato)aluminum complexes for the polymerisation of lactide.

Seven bis(pyrrolylaldiminato)aluminum methyl complexes were synthesized from the reactions of AlMe3 and two equiv. of the corresponding pyrrolylaldimine ligands. The ligands were modified to have different steric hindrances (C6H5 (1), 2,6-Me2C6H3 (2), 2,4,6-Me3C6H2 (3), 2,6-Et2C6H3 (4) and 2,6-(i)Pr2C6H3 (5)) and electronic contributions (4-CF3C6H4 (6) and 4-OMeC6H4 (7)).

Synthesis of cyclic polylactide catalysed by bis(salicylaldiminato)tin(II) complexes.

Eight bis(salicylaldiminato)tin(II) complexes have been synthesized from the reaction of Sn[N(SiMe(3))(2)](2) and 2 equiv of the corresponding ligands at room temperature. The ligands, synthesized from salicylaldehyde and amines, were designed to have different electronic and steric properties using different amines to synthesize the tin(II) complexes as aniline (2a), 2,6-dimethylaniline (2b), 2,6-diisopropylaniline (2c), 4-methoxyaniline (2d), 4-trifluoromethylaniline (2e), methylamine (2g), and tert-butylamine (2h). Ligand variation at the salicyl group synthesized from 4-bromosalicylaldehyde and 2,6-diisopropylaniline was used to form complex 2f.

Synthesis of high-molecular-weight poly(ε-caprolactone) catalyzed by highly active bis(amidinate) tin(II) complexes.

A series of bis(amidinate) tin(II) complexes is synthesized and shown to rapidly polymerize ε-caprolactone (ε-CL) in the presence and absence of benzyl alcohol giving high-molecular-weight poly(ε-CL) (M(n) up to 160,600 Da). Ligands having electron donating groups were found to accelerate the polymerization by making the complex more nucleophilic.

Reverse orders of reactivities in the polymerization of cyclic esters using N(2)O(2) aluminium alkoxide complexes.

Three aluminium alkoxide complexes containing N(2)O(2) bis(phenoxy)-amine ligands were synthesized from reactions of the corresponding N(2)O(2) ligands with Al(O(i)Pr)(3) in toluene. Different amine side chains of the ligands included pyridine (1), CH(2)NMe(2) (2), and CH(2)NEt(2) (3). The related chloro aluminium analog (4) was prepared from a reaction between AlCl(3) and the potassium salt of the N(2)O(2) ligand having CH(2)NMe(2) side chain.

Facile alcoholysis of L-lactide catalysed by Group 1 and 2 metal complexes.

Alkyl (S)-lactate and alkyl (S,S)-lactyllactate were rapidly and conveniently synthesized from L-lactide using Group 1 and 2 metal complexes as catalyst in alcohol.