ABSTRACT The first Pt II ···Au III metallophilic interaction is reported in K 4 [Pt(CN) 4 ][Au(CN) 4 ]Cl·6H 2 O, which consists of a 1D chain of stacking [Pt(CN) 4 ] 2− and [Au(CN) 4 ] − units bridged by potassium cations, with extremely short Pt II ···Au III distances of 3.0024(4) and 3.0057(4) Å at 80 K. The chloride ions and water molecules are bound to the potassium cation. Addition of KCl to the reaction mixture is necessary for the metallophilic Pt II ···Au III chain to assemble. The isostructural [Pd(CN) 4 ] 2− and [Ni(CN) 4 ] 2− analogs can be rationally synthesized in a similar manner, which feature the first Pd II ···Au III and Ni II ···Au III interactions, with the Ni II analog having the shortest metal‐metal distances of 2.968(3) and 2.978(3) Å. The bromide versions of all compounds were also synthesized by substituting KBr for KCl in the reaction mixture. 195 Pt solid‐state NMR of the title compound revealed highly anisotropic, axially symmetric magnetic shielding which resembles that found in systems with Pt II ···Pt II interactions, such as K 2 [Pt(CN) 4 ]·H 2 O. The Pd II and Pt II analogs are emissive, with λ max of 555 and 570 nm. Theoretical calculations indicate that the positive charge of the K + ions effectively neutralizes the electrostatic repulsion between the cyanometallates, resulting in significant metal‐based donor‐acceptor interactions. These novel d 8 ··· d 8 interactions provide a conceptual framework for the rational design of future metallophilic compounds.

The hydrolysis reaction of PcNbCl3 (Pc = phthalocyaninato) and PcNb(OiPr)3 produces the mu-oxo species [(PcNb)2(O)(mu-O)2] (and some Nb2O5), which was structurally characterized to reveal a dinuclear complex with two PcNb(V) units linked by two mu-oxo bridges; one of the Nb(V) centres has an additional terminal oxo ligand. [(PcNb)2(O)(mu-O)2] has an overall butterfly-shaped structure, with a dihedral angle of 31.1 degrees between the two Pc planes. Hydrolysis of PcZrCl2 in THF generated solutions that remained stable for months, but no crystalline material was isolated; alternatively, reaction with excess [nBu4N]F in DMSO produced soluble [nBu4N]PcZrF3, with a concomitant 16 nm shift in the Q-band position vs. PcZrCl2. [nBu4N]PcZrF3 was structurally characterized, revealing a mononuclear seven-coordinate PcZrF3-"ate" complex anion with the Zr(IV) centre protruding 1.25 & Aring; from the Pc-plane. In contrast, the reaction of PcZrCl2 with excess [nBu4N]Cl yielded [nBu4N]2[PcZr(OH2)4]Cl4, containing an eight-coordinate square-antiprismatic Zr(IV) centre bound by the four Pc-nitrogen donors on one side and a square arrangement of four aqua ligands on the other (approx. 45 degrees offset from the Pc-N bonds) to give a {PcZr(OH2)4}2+ core; the four chlorides reside in the secondary coordination sphere, hydrogen-bonding to the aqua ligands and yielding an overall "ate"-type {[PcZr(OH2)4]Cl4}2-complex anion. This indicates that fluoride addition preferentially generates Zr-F bonds via displacement of bound chloride or aqua/hydroxo units (in the absence of excess water), while on the other hand, Zr-OH2 coordination remains intact in the presence of excess chloride, reflecting the "hard" nature of the Zr(IV) centre.

Four new actinide coordination polymers utilizing cyanoaurate anions have been synthesized and characterized by single-crystal X-ray diffraction. The use of O-donor 4,4 '-bipyridine-N,N '-dioxide (bipyO2) ligands as neutral supports proved instrumental in the self-assembly of these frameworks, particularly given the high Lewis acidity of the Th(IV) centres. UO2(OH2)(bipyO2)2[Au(CN)2]2 & centerdot;3H2O (1) and Th(OH2)5(bipyO2)2[Au(CN)2]3 & centerdot;NO3 & centerdot;H2O & centerdot;CH3OH (3) have interpenetrated 2-D frameworks as well as tetrameric and polymeric Au(I) chains, respectively. [UO2(OH2)]2(bipyO2)5[Au(CN)4]4 (2) and Th(OH2)4(bipyO2)4[Au(CN)4]4 & centerdot;bipyO2 & centerdot;3H2O & centerdot;CH3OH (4) house their [Au(CN)4]- anionic aggregates within square vacancies in their cationic framework. The structural similarities between the Au(I) (1 and 3) and Au(III) (2 and 4) compounds demonstrate the effect these cyanometallates impose on the self-assembly process. To probe these supramolecular motifs, Hirshfeld surface analysis was used, demonstrating strong aurophilic interactions between [Au(CN)2]- anions alongside strong H & centerdot;& centerdot;& centerdot;N(cyano) hydrogen bonding anchoring with the surrounding framework. On the other hand, the [Au(CN)4]- anions formed weaker dative Au & centerdot;& centerdot;& centerdot;N(cyano) and H & centerdot;& centerdot;& centerdot;N(cyano) interactions with each other and the surroundings, respectively; the weaker and less directional interactions allowing molecular shape to play a larger role in influencing the framework structure.

We performed a comprehensive electrochemical and spectroelectrochemical study of three transition metal phthalocyanine (Pc) complexes, Pc n-OBu (2−)Mn III Cl, Pc tBu (2−)Mn III Cl and Pc tBu (2−)Cr III Cl (Pc tBu is the dianion of 2,9(10),16(17),23(24)-tetra- tert -butyl-phthalocyanine and Pc n-OBu is the dianion of 1,4,8,11,15,18,22,25-octa-n-butoxy-phthalocyanine), that are relevant for a variety of bond-breaking and forming reactions. Syntheses were optimized for previously reported tert -butylated species. Solvent-dependent voltammetry, spectroelectrochemistry, and for the first time for Mn III and Cr III Pc derivatives, spectroelectrochemical magnetic circular dichroism (MCD), were used to assess ligand- versus metal-centered redox events, electrochemical and chemical reversibilities of electron transfer, and effects of axial ligand coordination in dichloromethane or chloroform (DCM or CHCl 3 ) versus N,N -dimethylformamide (DMF). Comparisons are made to previously reported voltammetry and spectra of both Pc(2−)Mn II and chemically prepared oxidation states of Pc(2−)Cr II . We observe differences in localization of reduction events in P c n-OBu (2−)Mn III Cl versus Pc tBu (2−)Mn III Cl, with a more electron-rich ring promoting formation of MnI over Pc-centered reduction. We observe unique reduction behavior in Pc tBu (2−)Cr III Cl that points towards a mixture of ligand- and metal-centered character. To the best of our knowledge, these studies represent the first complete solvent-dependent spectroelectrochemical characterization of both Mn III and Cr III phthalocyanine derivatives across up to six different oxidation states.

The luminescent and magnetic properties of trivalent lanthanides (Ln3+) are indispensable for many emerging technologies, but exacting fine control over these properties requires an understanding of how to purposefully engineer the coordination geometry and site symmetry of Ln3+ centres. Here, we use the Cambridge Structural Database to extract the structures of 12,670 eight-coordinate Ln3+ centres and use Continuous Shape Measures, Continuous Symmetry Operation Measures, and a new structural similarity-based network analysis to survey geometry and structure trends. This survey is then leveraged to deliver concrete strategies for controlling the coordination geometry of eight-coordinate Ln3+ centres using familiar concepts like Ln3+ metal size and ligand denticity, bite angle, flexibility, shape, symmetry, and size. Ultimately, we present a roadmap for targeting each of the six common eight-coordinate geometries - hexagonal bipyramidal, cubic, square antiprismatic, dodecahedral, bicapped trigonal prismatic, and snub disphenoid - which are each demonstrated to have unique use-cases in diverse research areas. The effects of crystal packing and non-covalent interactions are also illustrated, allowing fine-grained control over the geometry and symmetry of Ln3+ centres. This work ultimately serves to inform the deliberate design of Ln3+ coordination complexes and materials for applications including data-storage, quantum information processing, lighting, thermometry, and medical bioimaging.

The synthesis, characterization, X-ray structures, and luminescence of a series of coordination polymers containing Group 1 and 2 metal cations with anionic gold(I) iso-maleonitriledithiolate units ([Au2(i-mnt)2]2-; {Au2[S2C = C(CN)2]2}2-) are described. Crystals of M(DMF)6[Au2(i-mnt)2] (M = Mg, Ca, Ba) contain 1-D aurophilic chains of [Au2(i-mnt)2]2- units. For M = Mg and Ca, the cations are DMF-saturated while for the M = Ba analogue a more complex network structure is formed whereby the N-cyano moieties from [Au2(i-mnt)2]2- bind to a dinuclear Ba(II) cluster with bound DMF units; the M = Sr system forms a related hydrate with similar dinuclear Sr(II) units which lie pendant to but not bridging the aurophilic chains. Crystals of the related Group 1-based materials, of the form M2(DMF)n[Au2(i-mnt)2] (M = Li, n = 6; K, n = 4; Cs, n = 3), also contain 1-D aurophilic chains, from which the N-cyano moieties of the i-mnt bind to the Group 1 metal centers; the lithium cations cap the N-cyano moieties, while potassium and cesium cations bridge the chains via more complex dinuclear [K2(DMF)4]2+ and [Cs4(DMF)6]4+ clusters respectively. The emission maxima, ranging from 570 - 670 nm are influenced by the intra- and intermolecular Au─Au distances as well as a combination of the Au─Au─Au angles and intra-ring torsion in the [Au2(i-mnt)2]2- units. The structural data illustrates a preference for N-cyano and cluster formation in the Group 1 and larger Group 2 metal centers and indicates a clear interplay between the obtained structural morphology and the size and charge of the cation.

A series of soluble ring-unsubstituted early-transition metallophthalocyanine (PcM) alkoxides with zirconium(IV) and niobium(V) metal centers was prepared via salt metathesis with PcM chlorides and a range of lithium or sodium alkoxides (NaOMe, NaOEt, LiOiPr, and NaOtBu); several examples were structurally characterized. Given their large ionic size, the metal centers protrude out of the Pc cavity, engendering cis-axial ligation of the alkoxides and thereby generating substantially improved solubility relative to the starting PcM chlorides. Seven-coordinate PcM(OR)3-type coordination spheres were typically observed, with lithium- or sodium-balanced "ate" species PcZr(OiPr)3Li(THF) and PcZr(OtBu)3Na(THF) isolated for PcZr(IV), compared to the neutral PcNb(OiPr)3. With the highly steric R = tBu the neutral six-coordinate PcZr(OtBu)2 was also structurally characterized. The catalytic activity of the PcZr(IV) and PcNb(V) alkoxides was probed toward the ring-opening polymerization (ROP) of rac-lactide, with PcZr(OiPr)3Li(THF) being the most active, while the PcNb(V) systems were either inactive or yielded oligomers.

The development of electrocatalysts that efficiently valorize carbon dioxide (CO2) is of ongoing interest. To that end, there is interest in the advancement of molecular catalysts that can promote reactions that address reaction bottlenecks. Examples of emerging catalyst designs include ligands with ancillary groups that support proton transfer reactions or ligands with charged groups that promote electrostatic interactions that facilitate key reaction steps. Such designs have considerably improved CO2 reduction rates with respect to unmodified parent complexes. However, examples where the ligand framework could provide more than one catalysis-assisting function are rare. Herein, we use a (diimine)Re(I)-fac(CO)3 complex with an N-methylated terpyridine ligand to demonstrate that the placement of a cationic and redox-active group proximal to the Re active sites can improve CO2 reduction rates. We observe a substantial improvement in observed rate constants with respect to the unmethylated terpy complex. However, the role of the methylpyridinium group is not as simple as pure redox mediation or electrostatic effects. Density functional calculations support the idea that both the redox reactivity of the entire ligand and the presence of only partial positive charge near the Re site can contribute to the observed CO2 reduction properties. The results are an example of how ligand designs that incorporate combinations of ancillary groups with different properties can be used to promote electrocatalytic reactions.

Effective personal protective equipment (PPE) and operational clothing and equipment (OCE) are essential to protect healthcare workers and the population at large from infectious microbes, as highlighted by the COVID-19 pandemic. The demand for effective and technologically advanced PPE/OCE is high due to the threat of new viral pandemics and growing antibiotic resistance. PPE and OCE typically act as physical barriers to respiratory droplets and other body fluids and thus are limited in their ability to protect users. Here we sought to develop PPE/OCE materials that actively kill bacteria and inactivate viruses upon contact. Photoactivatable metallophthalocyanines (PcMs) have antimicrobial properties and are more cost-effective and less toxic than metals and nanoparticles as surface treatments. We identified several PcMs with strong in-solution activity for both Gram-positive and Gram-negative bacterial pathogens and diverse viral pathogens. These PcMs were used to dye textiles and paper under mild conditions. Upon photoactivation cotton and paper dyed with the water-soluble PcM RLP068/OTf produce a 5-6-log10 reduction in viable Gram-positive bacteria, a 3-log10 reduction in Gram-negative bacteria, and a 1-2-log10 reduction in active enveloped viruses. A combination of RLP068/OTf and the water-insoluble PcM 4BuImid/OTf produced a 4-5-log10 reduction in both Gram-positive and Gram-negative bacteria. Leaching of these compounds into the surrounding medium is minimal, suggesting their microbicidal activity results from direct contact. The self-sterilizing textiles identified here are promising raw materials for low-cost PPE and OPE in preparation for pandemics and for everyday protection in sectors at high risk from pathogen transmission.

Using the ligand 2,2 ';6 ',2 ''-terpyridine-N,N',N"-trioxide (terpyO3), the series of hydrates [Eu(terpyO3)2]2(OH2)y(OH)[Au(CN)4]5 center dot xH2O (y = 3, x = 10, 1 center dot 13H2O; y = 3, x = 6, 1 center dot 9H2O; y = 2, x = 4, 1 center dot 6H2O; and y = 2, x = 1, 1 center dot 3H2O) was synthesized, with 1 center dot 13H2O crystallizing out of water, 1 center dot 9H2O forming after removal from the mother liquor, 1 center dot 6H2O forming at 60 degrees C, and 1 center dot 3H2O generated at 160 degrees C. The first three compounds were structurally characterized and feature large water clusters supported between the Eu-terpyO3 metal-ligand complexes, and 2-D or 1-D motifs of [Au(CN)4]- anions assembled via Au center dot center dot center dot N-cyano interactions. 1 center dot 3H2O was amorphous. Crystallographic evidence showed that the [Au(CN)4]- N-cyano groups replace Eu(III)-bound aqua ligands as dehydration proceeds. The photoluminescence properties of 1 center dot 9H2O and 1 center dot 3H2O show ligandsensitized Eu(III)-based emission with quantum yields of 20.5(11) and 49(2) % and lifetimes of 277.5(6) and 445(17) mu s, respectively, with these differences likely due to the decrease in number of OH oscillators nearby the Eu(III) centres in the lower hydrate form.

Interfacial electron transfer kinetics (IETK) are a crucial factor for many electrochemical applications, including redox flow batteries. Utilizing parameters such as the diffusion coefficient and heterogeneous standard rate constant, the mass transport and Butler-Volmer kinetics of a redox active molecule can be quantified. Many studies exist that describe the solvent effects of various electrolyte compositions on these redox active molecules. However, their structure-function relationship is seldom considered. Here in, we aim to explore the effects of metal polarizability and axial ligand occupancy on IETK for a series of 2,9,16,23-tetratertbutylmetallophthalocyanines using cyclic and rotating disk electrode voltammetry. Then determine how these differences in IETK transfer to redox flow battery performance to outline a guide for designing better active materials for these systems.

The mechanochemical synthesis of a family of heterobimetallic Ln(III)-M(II) coordination polymers of the form [Ln(OAc)2(OH2)3](MBr3)]·xH2O (Ln = Eu, Tb, 50:50 Eu/Tb; LnHg: M = Hg, x = 1; LnPb: M = Pb, x = 0) is described. They are formed via the anion-exchange reaction between lanthanide(III) bromide and metal(II) acetate salts and driven by a mismatch in hard-soft acid-base character. The crystal structure of EuHg revealed a heteropolymeric 1-D structure, with cationic acetate-bridged and anionic bromide-bridged chains forming parallel arrays; IR, Raman, and photoluminescence spectroscopic data of LnPb strongly suggested similarity with the LnHg compounds. The analogous reaction with EuCl3·6H2O and Hg(OAc)2 forms an isostructural material, but substituting Pb(OAc)2 generates [Eu(OAc)2(OH2)3]Cl and PbCl2 instead of a mixed-metal product comparable to LnPb. An N,N-dimethylformamide (DMF) solvate [Eu(OAc)2(DMF)3](PbBr3)] (EuPb·DMF) was structurally characterized, showing the same heteropolymeric motif as EuHg and resembling an organic-inorganic lead-halide perovskite due the anionic chain of face-sharing bromoplumbate(II) octahedra. Photoluminescence properties of the compounds, including lifetime measurements and Tb(III)→Eu(III) energy transfer parameters for the LnM 50:50 Eu/Tb solid-solutions are described.

Six sets of tetracyanoaurate(III) salts were synthesized and structurally characterized using the metal‐ligand complex cations [RE(bipyO 2 ) 4 ] 3+ (RE = Sc, Y, La; bipyO 2 = 2,2′‐bipyridine‐ N , N ’‐dioxide), [Fe(bipyO 2 ) 3 ] 3+ , [Ln(dmbipyO 2 ) 4 ] 3+ (Ln = Ce, Eu, Yb; dmbipyO 2 = 4,4′‐dimethyl‐2,2′‐bipyridine‐ N , N ’‐dioxide), [Ca(tcmc)] 2+ (tcmc = 1,4,7,10‐tetrakis‐(carbamoylmethyl)‐1,4,7,10‐tetraazacyclododecane), and [Ca(12‐crown‐4) 2 ] 2+ . Noncovalent assembly of the [Au(CN) 4 ] − anions tended to occur via Au···N cyano interactions; however, rare Au(III)···Au(III) contacts between the [Au(CN) 4 ] − groups — suggesting aurophilicity — could be induced when certain cation shape requirements were met. Specifically, cations with shape, size, and symmetry that allowed for packing in a complementary fashion with Au(III)···Au(III) aligned [Au(CN) 4 ] − dimers or trimers — providing efficiently close‐packed layers — were found to be sufficient for manifesting Au(III)···Au(III) contacts. Modifying the [RE(bipyO 2 ) 4 ] 3+ cation with peripheral methyl groups (the [Ln(dmbipyO 2 ) 4 ] 3+ cation) caused isoreticular replacement of a {[Au(CN) 4 ] 3 } 3− trimer with a dumbbell‐shaped {[Au(CN) 4 ] 2 Cl} 3− tri‐anion featuring an unusual Au···Cl···Au bridge — illustrating that the assembly of the anionic groups will adapt to conserve the same close packing. Au(III) aurophilicity between the [Au(CN) 4 ] − groups was studied using computational methods, crystal packing of the structures was probed using Hirshfeld surface analysis, and the emission properties of compounds containing the [Eu(dmbipyO 2 ) 4 ] 3+ luminophore were investigated, showing high quantum yields of ca . 50%.

A series of PcMn(III) complexes (Pc = phthalocyanine) was synthesized and structurally characterized by stripping the chloride from PcMnCl with AgSbF6 in ortho-dichlorobenzene (DCB) in the presence of DMSO or DMF; this yielded crystals of [PcMn(H2O)(2)]SbF6 & sdot;2DMSO and [PcMn(H2O)(2)]SbF6 & sdot;4DMF, respectively, which are insoluble in DCB. The use of AgOSO2CF3 (AgOTf), under similar conditions, yielded DCB-soluble PcMn(DMSO)OTf and PcMn(DMF)OTf, which were structurally characterized. Reacting PcMnCl with AgOTf in DCB, followed by addition of [(Bu4N)-Bu-n]OTf generated (Bu4N)-Bu-n[PcMn(OTf)(2)], which is air-stable and soluble in halogenated solvents; structural characterization revealed a six-coordinate Mn(III) "ate" complex with two trans-axially bound triflate anions. The PcMn(III) complexes are green in colour, with Q-band absorptions spanning from 722-739 nm and LMCT bands from 515-547 nm. Addition of neutral donors (THF, OPPh3, pyridine, DMSO, DMF) to (Bu4N)-Bu-n[PcMn(OTf)(2)] generated Q-band and LMCT peak shifts consistent with triflate substitution. These results show the utility of axially-bound triflate anions to increase PcM solubility, while still maintaining sufficient lability to permit reactivity at the axial site.

Ring-reduced and ring-oxidized boron subphthalocyanine complexes have been isolated and structurally characterized. The doubly reduced species forms a trinuclear cluster with intramolecular B-Nmeso bonds, while the mono-oxidized system shows minimal bond localization. UV-visible absorption spectra and accompanying TD-DFT calculations are indicative of the ring-oxidation state.

A common problem in fluorescence detection of gases like ammonia over a wide range from Parts Per Millions (ppm) to 10,000's ppm (similar to saturation) is that often over a 0-1000ppm range the spectrums show almost no visible changes. For many materials common detection methods like integrated emission, spectral subtraction, peak wavelength shift, peak intensity, FWHM, asymmetry all show only small fluorescent spectrum changes with ppm, typically shift <0.1% at 1000 ppm. Hence metrics more sensitive to subtle spectral changes are needed. We are exploring this with three different Vapochromic Coordination Polymers (VCP). which fluorescence when exposed to NH3 but in different ways: Zn[Au(CN)(2)](2), shifts its peak from 470-530nm under high concentration while peak intensity grows 3-5X, but shows tiny change <1000 ppm. Another VCP In-2[Pt(CN)(4)](3) shifts opposite, from 560 nm (yellow) to 530 nm but with even less change <1000ppm while Zn[Pt(CN)(4)] fluoresces at the short 430 nm.. To enhance subtle differences we use a 405nm laser diode excitation where the narrow 4nm stimulation does not mask short lambda contributions. Observing emission with a USB spectrometer we increase the slight spectra changes by dividing the spectrum into 10 nm bins, integrate the emission in each bin relative to that of 0 ppm exposure, then sum all the bins (Sum of Integrated Emissions, SIE). This emphasizes wavelength regions having rapid relative change at different ammonia ppm's. SIE gives excellent sensitivity in most ppm ranges, but at mid range 100-500 ppm regions it changes <1%: eg Zn[Au(CN)(2)](2), There some SIE bins decline while others increase due to the peak spectral shifts so it best to observe fewer SIE bins and look for ranges showing increasing values creating a second metric, Limited Range SIE, eg for Zn:Au 430-470nm bins show an accurate linear response. In many spectral fluorescence cases the region where the longer wavelength peak begins to dominate it is best to focus on regions outside of the peak maxim

Alternative energy sources have become critical to address climate change and global warming. Ammonia activation has been proposed as a solution to reduce CO 2 emissions, given ammonia's high hydrogen content and energy density, using transition metal electrocatalysis to oxidize ammonia as a hydrogen carrier, forming dinitrogen. Accordingly, a series of transition metal phthalocyanine complexes were selected as potential electrocatalysts for ammonia activation due to their wide range of metal (and ligand) oxidation states, rendering them excellent redox-active catalysts. Despite the inherent insolubility of phthalocyanine complexes, the addition of peripheral substituents can enhance their solubility, transforming them into effective homogeneous catalysts. In this research, we are investigating a series of octa-butoxy transition metal phthalocyanine complexes as electrocatalysts for ammonia activation. Initial studies have focused on interaction with NH 3 via UV-Vis spectroscopy and Electron Spray Ionisation-Mass Spectrometry, and electrochemically using cyclic voltammetry and differential pulse voltammetry. We will detail our results and research plans in this presentation.

Sandwich complexes usually have two similar ligands interacting with the central metal atom. In this work, a mixed sandwich with two different ligands, termed uranophthalocyanin-ocene U(COT)(Pc) (COT = cyclo-octatetraene2-; Pc = phthalocyaninato2-), has been synthesized from the reaction of UPcCl2·LiCl and K2COT. The crystal structure is reported, and the variable-temperature solid-state magnetic susceptibility measurements confirm the presence of a U(IV) center. This mixed-sandwich compound was compared to uranocene, U(COT)2, and bis(phthalocyaninato)uranium(IV), U(Pc)2, using density functional theory (DFT) and computational bonding analysis (ETS-NOCV). The geometrical structures have been optimized using DFT, and the obtained bond lengths are similar to the experimental results. From the energy decomposition analysis (EDA), it is evident that by replacing carbon atoms with nitrogen atoms, i.e., replacing COT with a Pc ligand, the covalent nature of the molecule increases.

A series of coordination polymers were synthesized by combining In(OTf)3 (OTf = trifluoromethanesulfonate), 2,2';6',2"-terpyridine (Terpy) or its substituted analogues 4'-amino-2,2';6',2"-terpyridine (NH2-Terpy), 4'-chloro-2,2';6',2"-terpyridine (Cl-Terpy), and 4'-bromo-2,2';6',2"-terpyridine (Br-Terpy), with K[Au(CN)2]. All compounds consist of 1D chains of hydroxy-bridged [In2(OH)2(X-Terpy)2]4+ dimers connected to a 1D chain of [Au(CN)2]- units featuring very short aurophilic interactions (3.0106(3)-3.2155(4) Å). The distance of the aurophilic interaction is directly tunable through minor modifications of the ligand, with the Au(I)···Au(I) distance increasing as the size of the substituent on the Terpy ligand increases. The compounds display photoluminescence emission maxima ranging from 600 to 650 nm, which are significantly lower energy than for most [Au(CN)2]--based materials. The emission maxima shift to higher energy as the aurophilic interactions become longer. These results demonstrate the ability to tune the Au(I)···Au(I) distance, and in turn the luminescence, by varying the size of the substituent on the chelating ligand.