Structural Chemistry最新文献

{"title":"New push–pull ladder-type chromophores with large hyperpolarizability for nonlinear optical application","authors":"Hejing Sun","doi":"10.1007/s11224-024-02348-8","DOIUrl":"https://doi.org/10.1007/s11224-024-02348-8","url":null,"abstract":"<p>A novel series of ladder-type chromophores TA0-5 with strong donor and acceptor were designed and theoretically investigated for applications in nonlinear optics. Chromophores TA0-5 possess ladder-type bridges with different fused-ring structures. The influence of varying structures of ladder-type bridges and introduction of strong donor and acceptor on the first hyperpolarizabilities in this innovative push–pull fused system were analyzed by multiple methods, such as (hyper)polarizability density, coupled perturbed Kohn–Sham (CPKS) method, sum-over-states (SOS) model and two states model. Through density of states analysis, TA0–TA5 all show deep HOMO levels and low energy gaps, indicating the excellent air-stable property of them. Through tuning the number of thiophene rings in the bridge and introduction of strong push–pull architecture, the first hyperpolarizabilities of new chromophores are significantly enhanced. Importantly, TA5 exhibits remarkable first hyperpolarizability ( <i>β</i>_tot value is 5882.1 × 10⁻³⁰ esu) in AN. The two-dimensional second-order nonlinear optical (NLO) spectra predicted by the SOS model show the strong NLO responses under external fields. All the designed chromophores exhibit outstanding electro-optical Pockels and optical rectification effects. The results reveal that this new series of push–pull ladder-type chromophores can be high-performance NLO materials and are expected to be prevalent for NLO and optoelectronic application.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"23 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141257598","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chérif F. Matta, Lulu Huang, Lou Massa, Quantum crystallography","authors":"Istvan Hargittai","doi":"10.1007/s11224-024-02336-y","DOIUrl":"10.1007/s11224-024-02336-y","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 4","pages":"1341 - 1343"},"PeriodicalIF":2.1,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141257693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Zn(II)-based 1D Coordination Polymer with Adsorption Properties and Hirshfeld Surface Analysis","authors":"Safarov Azamat Rasulovich,&nbsp;Ibragimov Aziz Bakhtiyarovich,&nbsp;Ruzmetov Abror Khamidjanovich,&nbsp;Normamatov Adkhamjon Sadullayevich,&nbsp;Yakubov Yuldosh Yusupboyevich,&nbsp;Abdullaev Ahrorjon Khabibjonovich,&nbsp;Adizov Bobirjon Zamirovich,&nbsp;Eshmetov Izzat Dosimbatovich,&nbsp;Muhammad Nadeem Akhtar,&nbsp;Ibragimov Avazbek Bakhtiyarovich,&nbsp;Ashurov Jamshid Mengnorovich","doi":"10.1007/s11224-024-02340-2","DOIUrl":"10.1007/s11224-024-02340-2","url":null,"abstract":"<div><p>A polymeric coordination compound [Zn₂₍PABA)₂(H₂O)₂Cl₂]_n (<b>1</b>) (where PABA is para-aminobenzoic acid) has been synthesized and characterized. We examined and explicated the porosity of the compound and employed a low-temperature nitrogen adsorption technique at 77 kelvins. Throughout the experiments, the nitrogen partial pressure ranged from 0.005 to 0.995 P/P⁰, aligning with the nitrogen adsorption and desorption curves. The surface area (SBET) was found to be 1945.72 m²/g with a micropore area of 361.56 m²/g that ensures the material’s ability to effectively adsorb small molecules. The nitrogen adsorption behavior on this compound is not only facilitates a deeper comprehension of its textural and structural attributes but also unveils potential applications, especially in pharmaceutical domains. Additionally, Hirschfeld surface analysis was performed, yielding interatomic interaction percentages on the Hirschfeld surface.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"2021 - 2031"},"PeriodicalIF":2.1,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141257606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Counter ions in tuning the extended arrangements of pyrazolone-thiosemicarbazone-based Fe(III) complexes","authors":"Tesfay G. Ashebr,&nbsp;Ahlam I. Al-Sulami,&nbsp;Zhifang Ma,&nbsp;Xiao-Lei Li","doi":"10.1007/s11224-024-02342-0","DOIUrl":"10.1007/s11224-024-02342-0","url":null,"abstract":"<div><p>Herein, we report the syntheses, crystal structures, and magnetic properties of the title compounds [Fe(III)L₂]Cl·CH₃OH, <b>1</b> and [Fe(III)L₂]NH(C₂H₅)₃, <b>2</b> formulated from pyrazolone-based thiosemicarbazone ligand (L) at room temperature. Structurally, the Fe(III) spin centre was chelated under N₂O₂S₂ coordination environment and then completed by charge-neutralizing counter ions for charge balance, i.e., the anion chloride (Cl⁻) for <b>1</b> and the cation triethylammonium (NH(C₂H₅)₃⁺) for <b>2</b>. Interestingly, the counter ions guided extended arrangement facilitated by halogen bonding of the Cl⁻ and hydrogen bonding of the NH(C₂H₅)₃⁺ were mainly responsible for obtaining the diamond- and hexagonal-shaped spin centre arrangements for <b>1</b> and <b>2</b>, respectively. Magnetic examination revealed that both compounds are high-spin (HS) at all the measurement temperature ranges, and the experimental bond distances (at 300 K) were also in good agreement for the HS state. Strong ligand field chemical modification on the ligand that stabilizes the low spin (LS) state is suggested to realize the spin crossover (SCO) phenomenon. Moreover, further biological and catalytic investigation of the reported new compounds is suggested, as thiosemicarbazone-containing HS metal complexes are good candidates for these applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"2015 - 2020"},"PeriodicalIF":2.1,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141257318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical study on the conformation and aromaticity of [13] to [33] double-stranded cyclophanes encompassing three benzene subunits","authors":"Mahsa Afshari,&nbsp;Hossein Fallah-Bagher-Shaidaei,&nbsp;Mohammad Nikpassand","doi":"10.1007/s11224-024-02347-9","DOIUrl":"10.1007/s11224-024-02347-9","url":null,"abstract":"<div><p>In the present study, conformations and aromaticity of seventeen [1₃], [2₃] and [3₃] double-stranded cyclophanes composed of three benzene moieties were investigated at <i>B3LYP</i> level of density functional theory. The stability of these conformers is different depending on the type of cycloalkane-like cycles formed by (CH₂) _n bridges and the peripheral benzene rings, and also the curvature of the latter. In [1₃] cyclophane, this leads to only one conformer containing puckered cyclobutane-like cycle, at an angle of about 37^◦. In comparison, in cyclophanes [2₃] and [3₃], the corresponding cycles are cyclohexane-like and cyclooctane-like, respectively. While conformer <b>2a</b> having TB-like cycles is the most stable member of the [2₃] family, of eight ground-state conformers obtained for [3₃], <b>3a</b> with two Chair-Chair-like and one Twist-Chair-like cycles is the most stable one, and <b>3h</b> with three Twist-Boat-like cycles being 6.5 kcal higher in energy than the former is the least stable member of series. In addition to the conformational analysis, the aromaticity of the series has been assessed using different indexes, including magnetic criteria nucleus-independent chemical shifts (NICS-based) at the cage and at the ring centers, HNMR chemical shift, Magnetic Susceptibility, HOMA and relative energy (RE).</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"2001 - 2013"},"PeriodicalIF":2.1,"publicationDate":"2024-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141197654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic structures of two-dimensional π-conjugated boroxine covalent organic frameworks","authors":"Qi Qi,&nbsp;Li Junfeng,&nbsp;Sun Yueming","doi":"10.1007/s11224-024-02344-y","DOIUrl":"10.1007/s11224-024-02344-y","url":null,"abstract":"<div><p>Boroxine covalent organic frameworks (boroxine COFs) can be referred to as two-dimension (2D) polymer networks with cores of boroxine connected with rigid linker and extended in x or y dimensions, which might be good candidates for organic electronic and luminescence material. However, the engineering COFs with improved charge transfer and conduction properties based on pore size and linker structure still confront various challenges. Here, we investigate the geometrical structure and electronic properties with linkers from phenyl to biphenyl and the replacement of H with F atom in 2D scale with the CRYTSTAL17 software at the density functional theory (DFT) level with the global-hybrid PBE0 functional and POB-TZVP basis set, using a 5 × 5 k-point mesh. The increased pore diameter reduced their energy gap. Replacing the F atom with the H atom lowered their VBMs and conduction band minimums (CBMs). Computation results can assist the experimental scientist in producing highly conductive 2D boroxine COFs.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1991 - 2000"},"PeriodicalIF":2.1,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141165395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel(II) complexes with a tetraazamacrocyclic diene ligand and its isomeric 'ane' forms: Synthesis, characterization, and antibacterial activities","authors":"Adrity Baidya,&nbsp;Pradip Paul,&nbsp;Saswata Rabi,&nbsp;Avijit Chakraborty,&nbsp;Benu K. Dey,&nbsp;Zinnat A. Begum,&nbsp;Ismail M. M. Rahman,&nbsp;Tapashi Ghosh Roy","doi":"10.1007/s11224-024-02332-2","DOIUrl":"10.1007/s11224-024-02332-2","url":null,"abstract":"<div><p>Applications of macrocyclic compounds and their various metal complexes in biological fields have notably increased. Therefore, it is reasonable to synthesize novel macrocyclic compounds and assess their biological properties. In this research, several new Ni(II) complexes were prepared using hexamethyltetraaza macrocycles, and their biological activity was studied. Specifically, a fourteen-membered tetraaza macrocyclic diene ligand in its dihydroperchlorate form, Me₆[14]diene⋅2HClO₄ (L⋅2HClO₄), along with its isomers tet-a and tet-b in their saturated ‘ane’ forms, were employed for complexation with Ni(II) acetate, followed by the addition of NaClO₄. The process resulted in the formation of square planar [Ni[(L´)](ClO₄)₂ (L´ = L, tet-a, or tet-b) and octahedral [Ni(tet-b)(ClO₄)₂] complexes. Furthermore, axial addition reactions involving SCN^–, Cl^–, Br^–, and I^– with [Ni[(L´)](ClO₄)₂ led to the formation of six-coordinated octahedral complexes, including [Ni(L)(NCS)₂], [Ni(tet-a)(NCS)₂], [Ni(tet-b)(NCS)₂] [Ni(tet-b)Cl₂], [Ni(L)Br₂], [Ni(tet-b)Br₂] and [Ni(tet-b)I₂]. Additionally, axial substitution reaction on the complex [Ni(tet-b)(ClO₄)₂] with SCN^– produced a five-coordinated square pyramidal complex, [Ni(tet-b)(NCS)](ClO₄). Modern analytical and spectroscopic techniques were used to characterize these complexes. It was observed that these complexes exhibited different geometries and electrolytic properties in different organic solvents where the Ni(II) showed different coordination modes. These complexes also displayed moderate antimicrobial activity against various bacteria.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1981 - 1990"},"PeriodicalIF":2.1,"publicationDate":"2024-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141165831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystallization of chiral thiourea derivatives of 1-phenylethylamine: transfer of stable motifs from racemic to homochiral environment","authors":"Lyubov V. Frantsuzova,&nbsp;Daria P. Gerasimova,&nbsp;Kirill E. Metlushka,&nbsp;Elena K. Badeeva,&nbsp;Kristina A. Nikitina,&nbsp;Ruzal G. Zinnatullin,&nbsp;Kamil A. Ivshin,&nbsp;Olga N. Kataeva,&nbsp;Olga A. Lodochnikova","doi":"10.1007/s11224-024-02343-z","DOIUrl":"10.1007/s11224-024-02343-z","url":null,"abstract":"<div><p>In a series of three chiral thioureas with a 1-phenylethylamine fragment, none of the homochiral samples forms “true chiral” hydrogen-bonded motifs in the crystal, but forms dimers or chains with local symmetry from the interacting fragments, consistent with the racemic crystal pattern.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1963 - 1980"},"PeriodicalIF":2.1,"publicationDate":"2024-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141152719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancement of nonlinear optical response of 26Adamanzane by doping with alkali metals exohedrally and alkaline earth metals endohedrally: a DFT study","authors":"Rimsha Akbar,&nbsp;Areeba Asif,&nbsp;Nimra Maqsood,&nbsp;Muhammad Nouman","doi":"10.1007/s11224-024-02337-x","DOIUrl":"10.1007/s11224-024-02337-x","url":null,"abstract":"<div><p>The quest for nonlinear optical (NLO) crystals, which are essential for future optical understanding, detailed evaluations, and present laser gadgets, is a prominent concern in the materials investigation. In this systematic analytical evaluation, the optical, electrical, and nonlinear optical (NLO) parameters of 2⁶Adamanzne which was doped endohedrally with alkaline earth and exohedrally with alkali metals, resulted with nine electron-rich complexes Mº(2⁶ADZ)M (where (Mº = Be, Mg, Ca) and (M = Li, K, Na)), were designed. Geometrical, thermodynamic, and electronic computations executed through density functional theory (DFT) and 6-31G (d,p) basis set. All metals doped 2⁶ADZ are within the range of effective NLO materials such as a lowered band gap in the range of 6.22–3.86 eV which was very higher in case of pure surface. At the same level of theory, transition density matrix (TDM), non-covalent interaction analysis (NCI), and electron density distribution map (EDDM) were carried out. The NBO analysis anticipated the charge transfer between donor and acceptor moieties. Computational investigations like binding energy (<i>E</i>_b), interaction energy, and vertical ionization potential confirm the high stability of the proposed complexes. The UV-visible assessment reveals that all complexes are transparent in the ultraviolet range and have maximum absorptivity up to 1009 nm (visible and NIR range). Doping techniques in all complexes profoundly impacted the oscillator strength and dipole moment, leading to an escalating value of hyperpolarizability <i>β</i>_tot up to 421.042 × 10⁻³⁰ esu. The optical efficiency of proposed complexes is approximated by using the value of isotropic linear polarizability (<i>α</i>_iso) which is boosted from 2.538 × 10⁻³⁰ to 8.665 × 10⁻²³ esu. The strong optical response of Mº(2⁶ADZ)M suggests its potential as a promising candidate for nonlinear optics, paving the way for synthesizing additional materials with practical applications in optoelectronics.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1943 - 1962"},"PeriodicalIF":2.1,"publicationDate":"2024-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141107438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In memoriam: Peter Politzer: A life to be truly celebrated","authors":"Jane S. Murray","doi":"10.1007/s11224-024-02339-9","DOIUrl":"10.1007/s11224-024-02339-9","url":null,"abstract":"<div><p>Peter Politzer (1937–2022) grew up with no doubt in his mind that he would pursue a career in chemistry. His research interests ranged from theoretical concepts such as electronegativity and chemical hardness to applications of electrostatic potentials and average local ionization energies to molecular interactive behavior and bonding, as well as to the study of chemical reactions and the reaction force in a variety of disciplines, including energetic materials. He will be remembered as a world-renowned leader in halogen bonding and other <i>σ</i>-hole bonding interactions and other areas of theoretical and computational chemistry, with over 520 research publications in scientific journals and books, leaving quite a legacy, with a marked tendency toward simplicity.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 4","pages":"1335 - 1340"},"PeriodicalIF":2.1,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141147171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}