1D Hybrid Semiconductor Silver 2,6-Difluorophenylselenolate

Abstract

Organic−inorganic hybrid materials present new opportunities for creating low-dimensional structures with unique light−matter interaction. In this work, we report a chemically robust yellow emissive one-dimensional (1D) semiconductor, silver 2,6-difluorophenylselenolate�AgSePhF 2 (2,6), a new member of the broader class of hybrid low-dimensional semiconductors, metal−organic chalcogenolates. While silver phenylselenolate (AgSePh) crystallizes as a two-dimensional (2D) van der Waals semiconductor, introduction of fluorine atoms at the (2,6) position of the phenyl ring induces a structural transition from 2D sheets to 1D chains. Density functional theory calculations reveal that AgSePhF 2 (2,6) has strongly dispersive conduction and valence bands along the 1D crystal axis. Visible photoluminescence centered around λ p ≈ 570 nm at room temperature exhibits both prompt (110 ps) and delayed (36 ns) components. The absorption spectrum exhibits excitonic resonances characteristic of low-dimensional hybrid semiconductors, with an exciton binding energy of approximately 170 meV as determined by temperature-dependent photoluminescence. The discovery of an emissive 1D silver organoselenolate highlights the structural and compositional richness of the chalcogenolate material family and provides new insights for molecular engineering of low-dimensional hybrid organic−inorganic semiconductors.

Engineering Supramolecular Hybrid Architectures with Directional Organofluorine Bonds

“…The emergence of a new diffraction peak, a 1D crystal habit, and a new optical phenomena lead us to suggest 2FY is a distinct 1D phase of 2F. This has precedence in the literature for a doubly fluorinated silver 2,6 difluorophenylselenolate, [17] so we postulate that a similar phase is accessible for the singly fluorinated species.…”

“…[9][10][11][12] This unique arrangement of monolayer performance in 3D crystals and numerous opportunities for crystal engineering by metal, [13] chalcogen, [14,15] and ligand (organic group) substitution makes the system an ideal test platform for understanding the emergence of complex/function properties in hybrid quantum solids. [16,17] The C─F bond has previously been used as a noncovalent interaction for materials engineering, [18] and the complex behavior of dipolar-dipolar interactions realized in crystal systems has been recognized. [19,20] Bond-dipole interactions have been observed to be more complicated [21,22] than molecular dipolar interactions, which generally do not play a pivotal role in crystal packing.…”

Dimensionality Engineering of Lead Organic Chalcogenide Semiconductors

“…However, so far, the versatility of the coinage metal-based MOCs is limited by the large band gaps (due to the large energy mismatch between the atomic orbitals of silver/copper and sulfur/selenium) and low structural tunability. 15,16 To systematically study the optical properties of MOCs, it is crucial to establish rational principles to design and manipulate their structures and electronic properties.…”

“…Among them, coinage metal-based metal organic chalcogenides (MOCs) have received extensive interest, − especially the 2D silver phenylselenolate (AgSePh) and its derivatives with different organic ligands. − This class of 2D materials exhibits strong quantum confinement and tightly bound excitons as multiquantum well systems, leading to intriguing optical properties including blue photoluminescence (PL), fast exciton recombination, in-plane anisotropy, etc. However, so far, the versatility of the coinage metal-based MOCs is limited by the large band gaps (due to the large energy mismatch between the atomic orbitals of silver/copper and sulfur/selenium) and low structural tunability. , To systematically study the optical properties of MOCs, it is crucial to establish rational principles to design and manipulate their structures and electronic properties.…”

XFEL Microcrystallography of Self-Assembling Silver n-Alkanethiolates

“…Metal–organic chalcogenolates (MOChas) are self-assembling coordination polymers of a metal and an organic source of sulfur, selenium, or tellurium. Recently, compounds in this family have attracted interest for semiconducting properties, light–matter interactions, and catalytic activity. − Silver n- alkanethiolates − have drawn consistent interest as three-dimensional analogues to the well-studied self-assembled monolayers (SAMs) on silver and gold metal surfaces and for their antimicrobial activity . However, a lack of a single-crystal structure because of small crystal sizes is a common refrain in reports of these and related compounds.…”