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Sulfur‐coordinated coordination polymers (S−CPs) have unique optoelectrical properties that originate from infinite M−S bond networks. In this study, we synthesized and characterized two polymorphs of a two–dimensional (2D) Pb(II) S−CP with a formula of [Pb(tzdt)(OAc)] (Htzdt=1,3‐thiazolidine‐2‐thione, OAc=acetate). Our findings revealed that the thermodynamic product (KGF‐26) possesses quasi‐2D (−Pb−S−)n layers with weak nonbonded Pb−S bonds, whereas the kinetic product (KGF‐27) has intrinsic 2D (−Pb−S−)n layers with Pb−S bonds. The results of time‐resolved microwave conductivity measurements and first–principles calculations confirmed that KGF‐27 exhibits higher photoconductivity than KGF‐26, which establishes that the inorganic (−Pb−S−)n networks with Pb−S bonds are crucial for achieving high photoconductivity. This is the first experimental demonstration of the impact of the (−M−S−)n networks in S−CPs on photoconductivity through the comparison of crystal polymorphisms. [ABSTRACT FROM AUTHOR]

One-dimensional (1D) Cd(II) coordination polymers [Cd(x-SPhOMe)2]n (x = ortho, meta, and para; HSPhOMe = methoxybenzenethiol) containing inorganic 1D (–Cd–S–)n chains were synthesized. Among these, the KGF-31 polymer bearing para-SPhOMe featured a three-strand chain structure assembled via interchain S⋯S interactions and exhibited high photoconductivity and longevity. [ABSTRACT FROM AUTHOR]

Hexaazatriphenylene (HAT) derivatives have attracted wide attention because of their electron‐deficient nature and unique self‐assembly properties. In this work, a facile synthesis method for obtaining HAT derivatives with alternating electron‐withdrawing nitrile and electron‐donating alkoxy groups (HATCNOCn) is proposed. Crystal structure analysis indicated that HATCNOCn forms a one‐dimensional columnar structure via strong π–π interactions. Density functional theory calculations revealed that the edge of HATCNOCn is divided into positively and negatively charged sites owing to the presence of alternating nitrile and alkoxy groups, which would induce strong π–π interactions. Thermal analysis and polarizing optical microscopy revealed that HATCNOCn exhibits columnar liquid‐crystal phases. Time‐resolved microwave conductivity measurements further demonstrated the photoconductive nature of HATCNOCn. The proposed strategy could provide a new strategy for the design of novel organic semiconductive materials. [ABSTRACT FROM AUTHOR]

The article titled "Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on Photoconductivity" explores the different structures and properties of a 2D PbII coordination polymer with Pb-S bonds. The cover picture showcases two polymorphs of the polymer, with one being the thermodynamic product and the other being the kinetic product. The thermodynamic product consists of quasi-2D layers with weak, nonbonded Pb-S bonds, while the kinetic product contains intrinsic 2D layers with Pb-S bonds. The kinetic product exhibits higher photoconductivity due to the presence of the intrinsic 2D layers. The research article by D. Tanaka and co-workers provides more detailed information on this topic. [Extracted from the article]