Crystal Growth & Design最新文献

{"title":"Liquid Metal-Enabled Galvanic Electrocrystallization of Charge-Transfer Complexes","authors":"Mahroo Baharfar*,&nbsp;Jiancheng Lin,&nbsp;Mohamed Kilani,&nbsp;Kourosh Kalantar-Zadeh and Guangzhao Mao*,&nbsp;","doi":"10.1021/acs.cgd.4c0121210.1021/acs.cgd.4c01212","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01212https://doi.org/10.1021/acs.cgd.4c01212","url":null,"abstract":"<p >Charge-transfer complexes (CTCs), which comprise ordered assemblies of electron acceptor and donor units, represent a mature group of advanced materials. These structures offer unique features, such as intrinsic conductivity, one-dimensional morphology, and tailorable chemistry. To enable the exploitation of CTCs for real-world applications, we investigate CTC nucleation and growth and develop scalable manufacturing methods for their incorporation into electronic systems. In the present work, we combine the unique features of CTCs and liquid metals (LMs) to investigate the galvanic electrocrystallization of tetracyanoquinodimethane complexes with silver (AgTCNQ) and copper (CuTCNQ). The eutectic alloy of gallium and indium (EGaIn) has been shown to be effective in nucleating CTC crystals. EGaIn reduces TCNQ and accumulates metallic precursors at the LM/solution interface via galvanic reduction and stabilization of the metal oxide nanoparticles. This enables the efficient formation and growth of conductive CTC crystals on patterned electronics without the need for an external input. The AgTCNQ wirelike crystals could transfer the autogenous potential of EGaIn, leading to their decoration with Ag nanoparticles. The AgTCNQ crystals grow longer than the CuTCNQ crystals, enabling the interconnection of electronic tracks. This knowledge opens new pathways for scalable CTC crystallization and direct incorporation into electronic systems.</p><p >The autogenous potential generated at the interface of gallium (Ga)-based liquid metals is harnessed to trigger galvanic reduction reactions, leading to the formation of metal-tetracyanoquinodimethane charge-transfer complexes (CTCs). This liquid metal interface demonstrated exceptional properties, facilitating the nucleation and growth of CTC crystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10225–10234 10225–10234"},"PeriodicalIF":3.2,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01212","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Gas Adsorption in MUT-11: Insights from Theoretical Calculations and GCMC Simulations","authors":"Mozhgan Parsaei,&nbsp;Kamran Akhbari*,&nbsp;Emmanuel Tylianakis*,&nbsp;George E. Froudakis and Jonathan M. White,&nbsp;","doi":"10.1021/acs.cgd.4c0128510.1021/acs.cgd.4c01285","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01285https://doi.org/10.1021/acs.cgd.4c01285","url":null,"abstract":"<p >Effective separation of C₂H₂/CO₂, N₂/CO₂, and H₂/CO₂ is crucial yet difficult in industrial applications, such as petrochemical production, natural gas processing, and environmental management. The conventional approach of pore sieving faces significant challenges in distinguishing gases with similar properties. In this study, a three-dimensional metal–organic framework (MOF) based on cadmium, referred to as <b>MUT-11</b> ([Cd₂(DBrTPA)₂(DMF)₃]; where DBrTPA = 2,5-dibromoterephthalic acid), was synthesized using various synthetic methods and extensively characterized using multiple analytical techniques. Additionally, the stability of <b>MUT-11</b> was evaluated by subjecting it to different organic solvents. To investigate the adsorption properties of CO₂, C₂H₂, N₂, and H₂ gases in both pure and binary states, the <b>MUT-11</b> structure underwent rigorous simulation-based analysis employing grand canonical Monte Carlo (GCMC)) simulations. GCMC simulations were utilized to assess the structure’s effectiveness in adsorbing light gases and separating binary mixtures into their individual components under specific thermodynamic conditions. The structure proved to be very efficient in adsorbing at low pressure, CO₂, and C₂H₂ since the pores of the material are filled very early. Similar GCMC simulations were conducted on dual component mixtures of CO₂–H₂, CO₂–N₂, and CO₂–C₂H₂. <b>MUT-11</b> proved to be very selective for CO₂ over any other gas studied.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10299–10313 10299–10313"},"PeriodicalIF":3.2,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling the Composition of III–V Ternary Nanowires with Group V Depletion","authors":"Vladimir G. Dubrovskii*,&nbsp;","doi":"10.1021/acs.cgd.4c0133810.1021/acs.cgd.4c01338","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01338https://doi.org/10.1021/acs.cgd.4c01338","url":null,"abstract":"<p >It is well documented that the concentrations of highly volatile group V atoms in liquid droplets catalyzing the vapor–liquid–solid growth of III–V nanowires decrease in the quasi-instantaneous process of monolayer progression and can even drop to equilibrium at a stopping size. This effect has far-reaching implications in the nanowire morphology, crystal phase, and nucleation statistics but was never considered in the compositional modeling of ternary nanowires. Here, we present the first attempt of such modeling for wurtzite III–V nanowires based on group V intermix. We show that the liquid–solid distribution of such nanowires starts from the kinetics shape at nucleation and transitions to the equilibrium distribution at the stopping size. The vapor–solid distribution is fully determined by the initial liquid composition at nucleation and is reduced to a simple analytic shape under some reasonable assumptions. When the stopping size is smaller than the nanowire monolayer, our theory predicts spatially inhomogeneous composition across the nanowire axis. The model fits very well the available compositional data on InP_<i>x</i>As_1–<i>x</i>, GaP_<i>x</i>As_1–<i>x</i>, and InSb_<i>x</i>As_1–<i>x</i> nanowires grown with different catalysts and sheds more light on the compositional control over III–V ternary nanowires in general. These results provide a starting point for further advancements in understanding and modeling of the complex growth process with a time-scale hierarchy of quasi-instantaneous monolayer progression and slow refill from vapor.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10379–10392 10379–10392"},"PeriodicalIF":3.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural Elucidation of the 1D Cd(II) Coordination Polymer and Its Application in the Selective Detection of TNP and the Schottky Diode Device Fabrication","authors":"Arka Patra,&nbsp;Suprava Bhunia,&nbsp;Pubali Das,&nbsp;Gurupada Bairy,&nbsp;Partha Pratim Ray* and Chittaranjan Sinha*,&nbsp;","doi":"10.1021/acs.cgd.4c0100110.1021/acs.cgd.4c01001","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01001https://doi.org/10.1021/acs.cgd.4c01001","url":null,"abstract":"<p >Research on the application of photoluminescence activity in the sensing of ions/molecules and the conductive nature of coordination polymers has attracted attention in recent years as an objective for Sustainable Development Goals. In this context, we designed and synthesized a one-dimensional (1D) coordination polymer <b>{[Cd</b>_<b>2</b><b>(tppz)(2-ATPA)</b>_<b>2</b><b>(H</b>_<b>2</b><b>O)</b>_<b>2</b><b>]</b>·<b>(MeOH)</b>_<b>2</b><b>}</b><i>_<b>n</b></i> (<b>CP1</b>), bridged by 2,3,5,6-tetrakis(2-pyridyl)-pyrazine (tppz) and 2-amino terephthalic acid (H₂ATPA) to the Cd²⁺ center. Amine (–NH₂) and one of the carboxylate (–COO^–) groups from H₂ATPA bridged two adjacent Cd(II) centers, forming a 14-member metalla-macrocycle that propagates in a one-dimensional (1D) pattern. The overall charge of the coordination unit was balanced by that of the other free carboxylates (–COO^–) of the acid linker. The H-bonding between amine (–NH₂) and carboxylate (–COO^–) groups of the neighboring coordinating unit architects the supramolecular frameworks. Hirshfeld surface analysis also computed the incidence of various types of noncovalent interactions (C···C; Cd···N; Cd···H; H···H; C···N; C···O; N···O; O···O). The <b>CP1</b> in the dispersed phase displayed strong blue emission at 428 nm in an acetonitrile medium, which was quenched selectively by 2,4,6-trinitrophenol (TNP) without interference in the presence of 12 other nitroaromatic compounds (NACs). The estimated limit of detection (LOD) value was as low as 0.096 ppm (0.18 μM). The interaction between <b>CP1</b> and TNP was supported by the lifetime of the excited state of the composite (<b>CP1</b>+TNP) (8.17 ns), which is significantly higher than that of <b>CP1</b> (2.54 ns). This primarily confirmed the stability of the composite at the excited state (<b>CP1*</b>+TNP). Thus, the longer lifetime of the composite substantiated the possibility of dynamic quenching. Tauc’s plot using the absorption spectrum estimated an optical band gap of 4.11 eV (DFT computed, 3.86 eV), which implies the semiconducting nature of the material. The electrical conductivity was measured using an ITO/<b>CP1</b>/Al electrode, which determined the electrical conductivity of 3.76 × 10^–6 S m^–1 in the dark phase and increased to 6.01 × 10^–6 S m^–1 upon light irradiation. This result validated the photoresponsive device applications.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10171–10181 10171–10181"},"PeriodicalIF":3.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enclathration of Saturated Five-Membered Rings by Tricyclic Fused Host Systems","authors":"Brandon Barnardo*,&nbsp;Benita Barton,&nbsp;Mino R. Caira* and Eric C. Hosten,&nbsp;","doi":"10.1021/acs.cgd.4c0129010.1021/acs.cgd.4c01290","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01290https://doi.org/10.1021/acs.cgd.4c01290","url":null,"abstract":"<p >In this work, the tricyclic fused host systems <i>N</i>,<i>N′</i>-bis(9-phenyl-9<i>H</i>-xanthen-9-yl)butane-1,4-diamine (<b>H1</b>) and <i>N</i>,<i>N′</i>-bis(9-(naphthalen-1-yl)-9<i>H</i>-xanthen-9-yl)butane-1,4-diamine (<b>H2</b>) were investigated for their host potential for three saturated five-membered ring guest solvents, namely, tetrahydrofuran, tetrahydrothiophene, and pyrrolidine (THF, THT, and PYRR). Both host species successfully enclathrated these solvents, forming 1:2 host–guest complexes with each one. Guest competition experiments by means of the crystallization of <b>H1</b> from all combinations of equimolar guest mixtures demonstrated a host selectivity that increased in the order THT &lt; PYRR &lt; THF. However, analogous experiments with <b>H2</b> only revealed a consistent preference for THT, while the selectivity for THF and PYRR depended on the number and types of guest species present. Nonequimolar binary guest experiments were also carried out, and these largely concurred with observations made in the equimolar guest experiments. SCXRD analyses demonstrated that <b>H1</b> retained its preferred guest compound, THF, in the crystal of the complex by means of a classical hydrogen bond (H···O, N···O, 2.31(3) Å, 3.193(4) Å, and 162(3)°), while THT (least favored) was involved in weaker (host)C–H···S–C(guest) and (host)N–H···S(guest) interactions (H···S, C···S, 2.91, 3.836 Å, 164°; H···S, N···S, 3.112, 4.027 Å, 168.92°, and 3.045, 3.971 Å, 174.65° for the two disorder guest components). <b>H2</b>, on the other hand, retained its preferred guest species (THT) in the complex by means of a singular short (guest)C–H···C–C(host) contact (C···H, C···C, 2.83, 3.754 Å, and 156°) which was absent in the inclusion compound containing disfavored THF. Moreover, also in this complex was identified a (host)N–H···S(guest) hydrogen bond (THF did not experience a hydrogen bond with <b>H2</b>); measurements were 3.468, 4.134 Å, and 135.38°. These observations align exactly with the guest preferences of these two host compounds. Hirshfeld surface considerations were employed to further explain these host behaviors in guest mixtures. Finally, thermal analyses were undertaken in order to determine the relative thermal stabilities of these complexes.</p><p >A (host)N−H···S(guest) hydrogen bond between host compound <i>N</i>,<i>N′</i>-bis(9-(napthalen-1-yl)-9<i>H</i>-xanthen-9-yl)butane-1,4-diamine (<b>H2</b>) and guest species tetrahydrothiophene (THT) facilitates the preference of <b>H2</b> for THT in tetrahydrofuran/THT/pyrrolidine mixtures.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10326–10337 10326–10337"},"PeriodicalIF":3.2,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01290","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lithium Ion Promoted the Formation of a Heat-Resistant Energetic Metal Salt with Dinitromethyl Functional Groups","authors":"Xianfeng Wang,&nbsp;Feng Yang,&nbsp;Jianshuo Cheng,&nbsp;Yuangang Xu,&nbsp;Qiuhan Lin,&nbsp;Pengcheng Wang and Ming Lu*,&nbsp;","doi":"10.1021/acs.cgd.4c0108810.1021/acs.cgd.4c01088","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01088https://doi.org/10.1021/acs.cgd.4c01088","url":null,"abstract":"<p >Heat-resistant explosives are indispensable compounds in the fields of energy exploitation and aviation. In this study, with 5-nitro-3-trinitromethyl-1,2,4-triazole as the raw material, an energetic metal salt dilithium 5-nitro-3-(dinitromethyl)-1,2,4-triazole (<b><i>DN-2Li</i></b>) with high thermal stability was obtained. The application evaluation parameters including thermal stability, mechanical sensitivity, and detonation performance were fully studied. The results show that <b><i>DN-2Li</i></b> not only has good detonation performance (<i>D</i>_v = 8669 m s^–1, <i>P</i> = 30.2 GPa) but also has appropriate mechanical sensitivity (IS = 4.0 J, FS = 100 N) and excellent thermal stability (<i>T</i>_d = 350.0 °C, <i>E</i>_K = 235.1 kJ mol^–1), which fully implies that <b><i>DN-2Li</i></b> has high application value as a heat-resistant explosive. This study not only provides a kind of heat-resistant explosive with potential application value but also provides a new vision for the design and preparation of new heat-resistant explosives.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10203–10208 10203–10208"},"PeriodicalIF":3.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stimuli-Responsive Lanthanide–Dianthracene Frameworks: Lanthanide-Dependent Photocycloaddition Reaction and Photophysical Properties","authors":"Qian-Qian Su,&nbsp;Song-Song Bao,&nbsp;Xin-Da Huang,&nbsp;Qian Teng,&nbsp;Xiu-Fang Ma,&nbsp;Ye-Hui Qin and Li-Min Zheng*,&nbsp;","doi":"10.1021/acs.cgd.4c0128710.1021/acs.cgd.4c01287","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01287https://doi.org/10.1021/acs.cgd.4c01287","url":null,"abstract":"<p >Metal–organic frameworks (MOFs) showing stimuli-responsive optical properties are very attractive due to their potential applications in information storage, molecular switches, and devices. In this work, we report a series of isomorphic lanthanide–dianthracene phosphonates with layered framework structures, namely, [Ln(NO₃)₃(depma₂)_1.5]·(depma₂)_0.5 (<b>1Ln</b>, Ln = Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb), where depma₂ stands for prephotodimerized 9-diethyl-phosphonomethylanthracene (depma). <b>1Ln</b> experiences a thermally induced single-crystal-to-single-crystal (SC–SC) structural transformation forming a chain compound [Ln(NO₃)₃(depma)(depma₂)]·(depma₂)_0.5 (<b>2Ln</b>) in which one depma₂ is dissociated into an anthracene pair. Interestingly, <b>2Ln</b> (Ln = Sm, Gd, Tb, Tm, Yb) exhibit excimer emission and undergo [4 + 4] photocycloaddition of anthracene in an SC–SC fashion to form the pristine <b>1Ln</b>, while the others either display a near-infrared (NIR) emission (for <b>2Nd</b>, <b>2Er</b>, <b>2Ho</b>) or nonemissive (for <b>2Eu</b>) and do not undergo photocycloaddition reaction. Obviously, reversible photoresponsive luminescence properties can be achieved for <b>2Ln</b> (Ln = Sm, Gd, Tb, Tm, Yb) but not for <b>2Ln</b> (Ln = Eu, Nd, Er, Ho).</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10314–10325 10314–10325"},"PeriodicalIF":3.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Use of Pseudosymmetry in the Design of Higher-Symmetry Crystals of Racemic Compounds.","authors":"Brent Lindquist-Kleissler, Viky Villanueva, Addis Getahun, Timothy C Johnstone","doi":"10.1021/acs.cgd.4c01240","DOIUrl":"10.1021/acs.cgd.4c01240","url":null,"abstract":"<p><p>Organometallic antimony(V) complexes were prepared as model compounds to better understand the interactions of chiral chelating diols with this metalloid. These complexes feature three aryl groups (<i>meta</i>-xylyl or <i>para</i>-tolyl) and a bidentate <i>trans</i>-2,3-butanediolate. The <i>meta</i>-xylyl and <i>para</i>-tolyl complexes of either enantiomerically pure 2<i>R</i>,3<i>R</i>-butanediolate or 2<i>S</i>,3<i>S</i>-butanediolate (compounds <b>1</b>-<b>4</b>) crystallized in Sohncke space groups, as expected. In each case, though, pseudoinversion centers were present that mimic higher-symmetry space groups through global pseudosymmetry. We hypothesized that the crystallization of 1:1 mixtures of the enantiomeric complexes would produce crystals in the centrosymmetric space group approximated by the pseudosymmetry. The enantiomerically pure <i>meta</i>-xylyl complexes each crystallized in space group <i>P</i>1 (approximating <i>P</i>1̅), and the racemic compound did indeed crystallize in <i>P</i>1̅. The enantiomerically pure <i>para</i>-tolyl complexes each crystallized in space group <i>P</i>2₁ (approximating <i>P</i>2₁/<i>c</i>), but the racemic compound crystallized in <i>P</i>1̅. Although the enantiomerically pure and racemic compounds are not isostructural, there are similarities in their 3D structures that are analyzed.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10247-10255"},"PeriodicalIF":3.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11660144/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic σ/π-Hole Interactions Directing Supramolecular Assembly: Tellurium···Platinum Chalcogen Bonding Enhanced by π-Stacking","authors":"Anastasiya A. Busygina,&nbsp;Anastasiya A. Eliseeva,&nbsp;Anton V. Rozhkov,&nbsp;Daniil M. Ivanov,&nbsp;Rosa M. Gomila,&nbsp;Antonio Frontera,&nbsp;Nadezhda A. Bokach* and Vadim Yu. Kukushkin*,&nbsp;","doi":"10.1021/acs.cgd.4c0123610.1021/acs.cgd.4c01236","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01236https://doi.org/10.1021/acs.cgd.4c01236","url":null,"abstract":"<p >This study investigates the synergistic effects of σ- and π-hole interactions in directing supramolecular assembly, focusing on unusual Te^II···Pt^II chalcogen bonding enhanced by π-stacking. Three novel cocrystals were synthesized and characterized, combining the dithiocarbamate complexes [Pt(ppy)(S₂CNC₆H₁₂)] and [Pt(ppy)(S₂CNC₄H₈)] (where ppyH = 2-phenylpyridine) with the tellurium(II)-based mixed σ/π-hole donors Te(C₅F₄N-4)₂ and Te(C₆F₄CF₃-4)₂. X-ray crystallography revealed a diverse array of noncovalent interactions, including two-center Te···Pt and three-center Te···(Pt,S) and Te···(Pt,C) chalcogen bonds, where the σ-Te^II-hole interacts directly with the <i>d</i>_<i>z</i>²-orbital of the positively charged platinum(II) ion. These unusual chalcogen bonds are significantly reinforced by π-stacking between the electron-deficient aromatic rings and platinum complex ligands. This combination of σ- and π-hole-based contacts leads to more robust and diverse supramolecular architectures compared to systems with isolated interactions. Theoretical calculations using QTAIM, NCIPlot, and NBO methods closely interrogated the interplay of these noncovalent forces highlighting the important role of electronic effects in controlling the balance between chalcogen bond and the π-stacking.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10235–10246 10235–10246"},"PeriodicalIF":3.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Use of Pseudosymmetry in the Design of Higher-Symmetry Crystals of Racemic Compounds","authors":"Brent Lindquist-Kleissler,&nbsp;Viky Villanueva,&nbsp;Addis Getahun and Timothy C. Johnstone*,&nbsp;","doi":"10.1021/acs.cgd.4c0124010.1021/acs.cgd.4c01240","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01240https://doi.org/10.1021/acs.cgd.4c01240","url":null,"abstract":"<p >Organometallic antimony(V) complexes were prepared as model compounds to better understand the interactions of chiral chelating diols with this metalloid. These complexes feature three aryl groups (<i>meta</i>-xylyl or <i>para</i>-tolyl) and a bidentate <i>trans</i>-2,3-butanediolate. The <i>meta</i>-xylyl and <i>para</i>-tolyl complexes of either enantiomerically pure 2<i>R</i>,3<i>R</i>-butanediolate or 2<i>S</i>,3<i>S</i>-butanediolate (compounds <b>1</b>–<b>4</b>) crystallized in Sohncke space groups, as expected. In each case, though, pseudoinversion centers were present that mimic higher-symmetry space groups through global pseudosymmetry. We hypothesized that the crystallization of 1:1 mixtures of the enantiomeric complexes would produce crystals in the centrosymmetric space group approximated by the pseudosymmetry. The enantiomerically pure <i>meta</i>-xylyl complexes each crystallized in space group <i>P</i>1 (approximating <i>P</i>1̅), and the racemic compound did indeed crystallize in <i>P</i>1̅. The enantiomerically pure <i>para</i>-tolyl complexes each crystallized in space group <i>P</i>2₁ (approximating <i>P</i>2₁/<i>c</i>), but the racemic compound crystallized in <i>P</i>1̅. Although the enantiomerically pure and racemic compounds are not isostructural, there are similarities in their 3D structures that are analyzed.</p><p >A panel of organometallic antimony(V) compounds is explored that bear chiral chelating diolate ligands. The enantiomerically pure compounds crystallize with pseudoinversion centers in a manner that mimics higher-symmetry space groups. We investigated whether the racemic compound would crystallize in this higher-symmetry space group.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 24","pages":"10247–10255 10247–10255"},"PeriodicalIF":3.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01240","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850931","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}