Variable-temperature Studies Research Articles

Propeller-Shaped Blatter-Based Triradicals: Distortion-Free Triangular Spin System and Spin-State-Dependent Photophysical Properties.

Herein, we report the synthesis and properties of triptycene-based C3v- and Cs-symmetric stable radical trimers. SQUID magnetometry showed the propeller-shaped trimers were both an antiferromagnetic equilateral triangle spin system with small spin-spin interaction J/kB ~ -120 K and -106 K, leading to ca. 4/6 coexistence of the doublet/quartet states in thermal equilibrium at room temperature. The trimers exhibited characteristic NIR absorption bands reaching 1000 nm, which was solely ascribed to the triradical in the doublet state by variable-temperature spectroscopic studies and quantum chemical calculations. Taking advantage of the spin-specific absorption feature, we found that the triradicals in the low-spin state undergo symmetry-breaking charge transfer, while those in the high-spin state fall into a monomer-like excited state.

Spectroscopic Properties and Reactivity of a MnIII-Hydroperoxo Complex that is Stable at Room Temperature.

Manganese catalysts that activate hydrogen peroxide have seen increased use in organic transformations, such as olefin epoxidation and alkane C-H bond oxidation. Proposed mechanisms for these catalysts involve the formation and activation of MnIII-hydroperoxo intermediates. Examples of well-defined MnIII-hydroperoxo complexes are rare, and the properties of these species are often inferred from MnIII-alkylperoxo analogues. In this study, we show that the reaction of the MnIII-hydroxo complex [MnIII(OH)(6Medpaq)]+ (1) with hydrogen peroxide and acid results in the formation of a dark-green MnIII-hydroperoxo species [MnIII(OOH)(6Medpaq)]+ (2). The formulation of 2 is based on electronic absorption, 1H NMR, IR, and ESI-MS data. The thermal decay of 2 follows a first order process, and variable-temperature kinetic studies of the decay of 2 yielded activation parameters that could be compared with those of a MnIII-alkylperoxo analogue. Complex 2 reacts with the hydrogen-atom donor TEMPOH two-fold faster than the MnIII-hydroxo complex 1. Complex 2 also oxidizes PPh3, and this MnIII-hydroperoxo species is 600-fold more reactive with this substrate than its MnIII-alkylperoxo analogue [MnIII(OOtBu)(6Medpaq)]+. DFT and time-dependent (TD) DFT computations are used to compare the electronic structure of 2 with similar MnIII-hydroperoxo and MnIII-alkylperoxo complexes.

Dual Emission with Efficient Phosphorescence Promoted by Intermolecular Halogen Interactions in Luminescent Tetranuclear Zinc(II) Clusters.

The development of Zn-based phosphorescent materials, associated with a ligand-centered (LC) transition, is extremely limited. Herein, we demonstrated dual emissions including fluorescence and phosphorescence in luminescent tetranuclear Zn(II) clusters [Zn4LI4(μ3-OMe)2X2] (HLI = methyl-5-iode-3-methoxysalicylate; X = I, Br, Cl), incorporating iodine-substituted ligands. Single-crystal X-ray structural analyses and variable-temperature emission spectra studies revealed the presence of iodine substitutions, and intermolecular halogen interactions produced the internal/external heavy-atom effects and yielded strong green phosphorescence with a long emission lifetime (λmax = 510-522 nm, Φem = 0.28-0.47, τav = 0.78-0.95 ms, at 77 K). This work provided a new example that the introduction of halogen interactions is an advantageous approach for inducing phosphorescence in fluorescent metal complexes.

Conversion of Metal Pyrazolate/(Hydr)oxide Clusters into Nanojars: Solution vs Solid-State Structure and Magnetism.

Nanojars are a class of anion binding and extraction agents composed of a series of [Cu(μ-OH)(μ-pz)]n (pz = pyrazolate; n = 26-36) supramolecular metal-organic complexes. In contrast to other anion binding agents amenable to liquid-liquid extraction, nanojars only form by self-assembly around the target anion, and guest-free nanojar hosts cannot be isolated. An extraordinary binding strength toward highly hydrophilic anions such as carbonate and sulfate was demonstrated by the inability of Ba2+ ions to precipitate the corresponding insoluble barium salts from nanojars. Herein, we provide an additional proof for the superior robustness of the nanojar framework based on competition experiments with other transition metal pyrazolate/(hydr)oxide complexes. In addition to the mass spectrometric characterization, we present variable-temperature nuclear magnetic resonance studies with an emphasis on the influence of the paramagnetic Cu2+ centers on 1H hyperfine shifts, along with X-ray crystallographic analysis of two polymorphs of (MePh3P)2[CO3⊂{Cu(OH)(pz)}27], including the highest (cubic) symmetry nanojar crystal lattice obtained to date as well as magnetism studies for the first time. Furthermore, we provide evidence for the first molybdate-incarcerating nanojars, [MoO4⊂{Cu(μ-OH)(μ-pz)}n]2- (n = 28, 31-33), formed by rearrangement from [MoVI8O12(μ-O)9(μ-pz)6(pzH)6·3pzH] in the presence of Cu2+ ions.

Facile construction of graphene oxide and iron organic frameworks decorated biopolymeric hybrid materials for fluoride uptake from water

The widespread excess level of fluoride in water causes a possible risk to human health. Herein, graphene oxide (GO) and iron-type metal–organic frameworks namely iron-benzene-1,4-dicarboxylate (Fe-BDC) supported material namely GO/Fe-BDC was employed to remove fluoride in water. Because of powder form, GO/Fe-BDC creates pressure drop during filtration. To overcome such troubles and improve fluoride adsorption capacity, GO/Fe-BDC integrated alginate (Alg) and chitosan (CS) biopolymer-based hybrid material namely GO/Fe-BDC/Alg-CS beads was developed for fluoride removal. Defluoridation properties of GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads were evaluated under numerous influencing conditions namely pH, contact time, variable fluoride concentration, co-ions, dosage and temperature studies. The GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads were revealed finer fluoride adsorption ability and also had high fluoride selectivity in complexed atmosphere with several co-ions. The element composition, crystalline nature and material morphology of GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads were characterized using SEM, XRD, FTIR and EDAX analysis. The order and nature of defluoridation was examined with kinetics, thermodynamic and isotherm analysis. The highest r values and lowest sd values exhibit that Langmuir adsorption isotherm and pseudo-second-order (PSO) models were consider as best fit models for fluoride adsorption process onto GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads. The thermodynamic results illustrate that fluoride adsorption was spontaneous, chemical adsorption with endothermic nature . Electrostatic interaction and complexation were found as the primary defluoridation mechanism of GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads. The renewal and field investigations of GO/Fe-BDC and GO/Fe-BDC/Alg-CS beads were explored to check their regeneration ability and field suitability nature.

C-H Bond Oxidation by MnIV-Oxo Complexes: Hydrogen-Atom Tunneling and Multistate Reactivity.

The reactivity of six MnIV-oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV-oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV-oxo complexes. These results are in accordance with the Bell model, where tunneling occurs near the top of the transition-state barrier. Density functional theory (DFT) and DLPNO-CCSD(T1) computations were performed for three of the six MnIV-oxo complexes to probe a previously predicted multistate reactivity model. The DFT computations predicted a thermal crossing from the 4B1 ground state to a 4E state along the C-H bond oxidation reaction coordinate. DLPNO-CCSD(T1) calculations further confirm that the 4E transition state offers a lower energy barrier, reinforcing the multistate reactivity model for these complexes. We discuss how this multistate model can be reconciled with recent computations that revealed that the kinetics of C-H bond oxidation by this set of MnIV-oxo complexes can be well-predicted on the basis of the thermodynamic driving force for these reactions.

Synthesis and Dynamic Behavior of Ce(IV) Double-Decker Complexes of Sterically Hindered Phthalocyanines.

Phthalocyanines and their double-decker complexes are interesting in designing rotative molecular machines, which are crucial for the development of molecular motors and gears. This study explores the design and synthesis of three bulky phthalocyanine ligands functionalized at the α-positions with phenothiazine or carbazole fragments, aiming to investigate dynamic rotational motions in these sterically hindered molecular complexes. Homoleptic and heteroleptic double-decker complexes were synthesized through the complexation of these ligands with Ce(IV). Notably, CeIV(Pc2)2 and CeIV(Pc3)2, both homoleptic complexes, exhibited blocked rotational motions even at high temperatures. The heteroleptic CeIV(Pc)(Pc3) complex, designed to lower symmetry, demonstrated switchable rotation along the pseudo-C4 symmetry axis upon heating the solution. Variable-temperature 1H-NMR studies revealed distinct dynamic behaviors in these complexes. This study provides insights into the rotational dynamics of sterically hindered double-decker complexes, paving the way for their use in the field of rotative molecular machines.

Controlling Adsorption of Diblock Copolymer Nanoparticles onto an Aldehyde-Functionalized Hydrophilic Polymer Brush via pH Modulation.

Sterically stabilized diblock copolymer nanoparticles with a well-defined spherical morphology and tunable diameter were prepared by RAFT aqueous emulsion polymerization of benzyl methacrylate at 70 °C. The steric stabilizer precursor used for these syntheses contained pendent cis-diol groups, which means that such nanoparticles can react with a suitable aldehyde-functional surface via acetal bond formation. This principle is examined herein by growing an aldehyde-functionalized polymer brush from a planar silicon wafer and studying the extent of nanoparticle adsorption onto this model substrate from aqueous solution at 25 °C using a quartz crystal microbalance (QCM). The adsorbed amount, Γ, depends on both the nanoparticle diameter and the solution pH, with minimal adsorption observed at pH 7 or 10 and substantial adsorption achieved at pH 4. Variable-temperature QCM studies provide strong evidence for chemical adsorption, while scanning electron microscopy images recorded for the nanoparticle-coated brush surface after drying indicate mean surface coverages of up to 62%. This fundamental study extends our understanding of the chemical adsorption of nanoparticles on soft substrates.

A Steric-Repulsion-Driven Clutch Stack of Triaryltriazines: Correlated Molecular Rotations and a Thermoresponsive Gearshift in the Crystalline Solid.

We report that a newly developed type of triaryltriazine rotor, which bears bulky silyl moieties on the para position of its peripheral phenylene groups, forms a columnar stacked clutch structure in the crystalline phase. The phenylene units of the crystalline rotors display two different and interconvertible correlated molecular motions. It is possible to switch between these intermolecular geared rotational motions via a thermally induced crystal-to-crystal phase transition. Variable-temperature solid-state 2H NMR measurements and X-ray diffraction studies revealed that the crystalline rotor is characterized by a vertically stacked columnar structure upon introducing a bulky Si moiety with bent geometry as the stator. The structure exhibits correlated flapping motions via a combination of 85° and ca. 95° rotations between 295 and 348 K, concurrent with a negative entropy change (ΔS‡ = -23 ± 0.3 cal mol-1 K-1). Interestingly, heating the crystal beyond 348 K induces an anisotropic expansion of the column and lowers the steric congestion between the adjacent rotators, thus altering the correlated motions from a flapping motion to a correlated 2-fold 180° rotation with a lower entropic penalty (ΔS‡ = -14 ± 0.5 cal mol-1 K-1). The obtained results of our study suggest that the intermolecular stacking of the C3-symmetric rotator driven by the steric repulsion of the bulky stator represents a promising strategy for producing various correlated molecular motions in the crystalline phase. Moreover, direct and reversible modulation of the intermolecularly correlated rotation is achieved via a thermally induced crystal-to-crystal phase transition, which operates as a gearshift function at the molecular level.

A [CoSiH2] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes.

Base-stabilized [BP3iPr](H)2CoSiH2(DMAP) (1, [BP3iPr] = PhB(CH2PiPr2)3-; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest "parent" silylene complex (LM═SiH2). Complex 1 was accessed in high yields via double Si-H bond activation in SiH4 by [BP3iPr]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si-H bonds of the SiH2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCoI)2(μ-N2) (L = a tripodal ligand) resulted in the spontaneous formation of [BP3iPr](H)2Co═Si═Co(H)2L (L = [BP2tBuPz], PhB(CH2PtBu2)2(pyrazolyl)- (3); Tp″, HB(3,5-diisopropylpyrazolyl)3- (4)) with the concomitant release of DMAP. The symmetrical silicide [BP3iPr](H)2Co═Si═Co(H)2[BP3iPr] (5) was prepared by treatment of a mixture of 1 and [BP3iPr]Co(DMAP) with 2 equiv of Ph3B, which in this case is required to sequester DMAP as the elimination product Ph3B-DMAP. A heterobimetallic silicide, [BP3iPr](H)2Co═Si═Fe(H)2[SiP3iPr] (7; [SiP3iPr] = PhSi(CH2PiPr2)3), was obtained via in situ KC8 reduction of [SiP3iPr]FeCl and subsequent addition of 1 and Ph3B. These transformations involving a metal-SiH2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.

CAT on MOUSE: Control and automation of temperature for single-sided NMR instruments such as NMR-MOUSE.

Temperature-dependent experiments are a rapidly growing area of interest for low-field NMR. In this work, we present a new device for wide-range temperature control for single-sided NMR instruments. The presented device, called CAT, is simple to build, inexpensive, and easy to modify to accommodate different samples. We present the capabilities of the device using a freezing temperature study of acetic acid/water mixtures. Additionally, we present the stability of the device over long measurement times. We believe that by introducing such a device with an open-source design, we allow researchers to use it in a wide range of applications and to fully incorporate variable-temperature studies in the world of single-sided instruments.

Fast and Tunable Phosphorescence from Organic Ionic Crystals.

Crystalline diphosphonium iodides [MeR2P-spacer-R2Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λem values from 550 to 880 nm) and intensities (Φem reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions. Time-resolved and variable-temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46-92.23 μs at 297 K. Radiative rate constants kr as high as 2.8 × 105 s-1 deduced for salts 1-3 were assigned to strong spin-orbit coupling enhanced by an external heavy atom effect arising from the anion-π charge-transfer character of the triplet excited state. These rates of anomalously fast metal-free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.

Switching On/Off of a Solvent Coordination in a Au(I)-Pb(II) Complex: High Pressure and Temperature as External Stimuli.

The benzonitrile solvate {[{Au(C6F5)2}2{Pb(terpy)}]·NCPh}n (1) (terpy = 2,2':6',2″-terpyridine) displays reversible reorientation and coordination of the benzonitrile molecule to lead upon external stimuli. High-pressure X-ray diffraction studies between 0 and 2.1 GPa reveal a 100% of conversion without loss of symmetry, which is totally reversible upon decompression. By variable-temperature X-ray diffraction studies between 100 and 285 K, a partial coordination is achieved.

An Old Crystallization Technique as a Fast, Facile, and Adaptable Method for Obtaining Single Crystals of Unstable "Li2TCNQF4" and New Compounds of TCNQ or TCNQF4: Syntheses, Crystal Structures, and Magnetic Properties.

Detailed structural information is essential for understanding the properties of TCNQ and TCNQF4 compounds (TCNQ = 7,7,8,8-tetracyanoquinodimethane; TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The ineludible requirement of obtaining crystals of a size and quality sufficient to yield a successful X-ray diffraction analysis has been challenging to satisfy because of the instability of many of these compounds in solution. Crystals of two new complexes of TCNQ, [trans-M(2ampy)2(TCNQ)2] [M = Ni (1), Zn (2); 2ampy = 2-aminomethylpyridine], as well as unstable [Li2(TCNQF4)(CH3CN)4]·CH3CN (3), can be prepared in minutes by a horizontal diffusion technique and can be harvested easily for X-ray structural studies. Compound 3, previously described as "Li2TCNQF4," forms a one-dimensional (1D) ribbon. Compounds 1 and 2 can also be obtained as microcrystalline solids from methanolic solutions of MCl2/LiTCNQ/2ampy. Their variable-temperature magnetic studies confirmed a contribution of strongly antiferromagnetically coupled pairs of TCNQ•- anion radicals at higher temperatures with exchange coupling J/kB = -1206 K and J/kB = -1369 K for 1 and 2, respectively, estimated using a spin dimer model. The presence of magnetically active anisotropic Ni(II) atoms with S = 1 in 1 was confirmed, and the magnetic behavior of 1, representing an infinite chain of alternating S = 1 sites and S = 1/2 dimers, was described by a spin-ring model suggesting ferromagnetic exchange coupling between Ni(II) sites and anion radicals.

Scissor-like Au4Cu2 Cluster with Phosphorescent Mechanochromism and Thermochromism

Reaction of [Au(tht)2](ClO4) (tht = tetrahydrothiophene), [Cu(CH3CN)4](ClO4), 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H3decz), and bis(2-diphenylphosphinophenyl)ether (POP) in the presence of triethylamine (NEt3) gave the cluster complex Au4Cu2(decz)2(POP)2 as yellow crystals. As revealed by X-ray crystallography, the Au4Cu2 cluster exhibits scissor-like structure sustained by two decz and two POP ligands and stabilized by Au-Cu and Au-Au interactions. The Au4Cu2 cluster shows bright yellow to orange photoluminescence upon irradiation at >300 nm, arising from 3[π (decz)→5d (Au)] 3LMCT (ligand-to-metal charge transfer) and 3[π→π* (decz)] 3IL (intraligand) triplet states as revealed by theoretical and computational studies. When it is mechanically ground, reversible phosphorescence conversion from yellow to red is observed owing to more compact molecular packing and thus stronger intermetallic interaction. Variable-temperature luminescence studies reveal that it displays distinct red-shifts of the emission whether the temperature is elevated or lowered from ambient temperature, suggestive of exceptional thermochromic phosphorescence characteristics.

Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers.

Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.

Solvent Coligand-Induced Spin State Variation in Iron(II) Complexes Bearing Pentadentate N5 Ligand Toward the Construction of an N5O Spin Crossover Center

Three iron(II) complexes having a 1,2,3-triazole-containing linear pentadentate N5 ligand L3-Me-3Me and different monodentate solvent coligand X, [Fe(L3-Me-3Me)X](BPh4)2 [L3-Me-3Me = bis(N,N′-1-methyl-1H-1,2,3-triazol-4-yl-methylideneaminopropyl)methylamine; X = MeCN (1), dimethylformamide (DMF) (2), and dimethyl sulfoxide (DMSO) (3)] have been selectively prepared by the choice of reaction solvent. Along the well-known spectrochemical series, the strong-field solvent ligand MeCN generates a low-spin (LS) complex 1, the weak-field ligand DMSO generates a high-spin (HS) complex 3, and the complex 2 coordinated by the medium-field ligand DMF exhibits gradual and reversible one-step HS↔LS spin crossover (SCO) with T1/2 = 173 K in the temperature range of 400–5 K. This spin state variation among LS 1, HS 3, and SCO 2 has been investigated by the combination of temperature-dependent magnetic susceptibilities measurements, single-crystal X-ray diffraction (SCXRD) studies, Hirshfeld surface analyses, and density functional theory calculations. In addition, the details of structural change between HS and LS states of an N5O iron(II) center upon SCO are revealed for the first time by the variable-temperature SCXRD studies for 2 at nine different temperatures in which the difference of Fe–O bond length between the two spin states is shorter than that of any other Fe–N bond lengths.

Crystal engineering, electron density analysis, andin situvariable temperature studies on co-crystal between nicotinic acid and gallic acid sesquihydrate

The growth and thermal stability of the gallic acid : nicotinic acid cocrystal has been analyzed in terms of electron density analysis and conversion of GA monohydrate into anhydrate through heating the co-crystal.

A tetracobalt(II) cluster with a two vertex truncated dicubane topology endogenously supported by carboxylate-based (2-pyridyl)methylamine ligands: magneto-structural and DFT studies.

A reaction between CoCl2 and L3-(CO2-)2 (2 : 1 stoichiometry) in CH3OH affords a discrete complex [CoII4-{L3-(CO2-)2}2(μ3-OCH3)2(CH3OH)2(H2O)2Cl2] (1) [L3-(CO2-)2 = 3-[N-{2-(pyridin-2-yl)methyl}amino]-bis(propionate)]. The structure of 1 reveals two terminal mononuclear CoII{L3-(CO2-)2}Cl units connected by a dimeric CoII2(μ3-OCH3)2(CH3OH)2(H2O) unit present in the centre through two methoxo (μ3-OCH3)- and two carboxylate (μ-1,1-OCO-) bridges affording a tetranuclear coordination cluster of Co(II) with a defective dicubane topology. In 1, Co1 (terminal) has distorted octahedral CoIIN2O3Cl and the central Co2 has CoIIO6 coordination. Such coordination arrangements afford the observed topology. Variable-temperature magnetic studies reveal anti-ferromagnetic coupling in 1. Three magnetic exchange interactions (one anti-ferromagnetic and two ferromagnetic: J1 = +3.3 cm-1 (Co⋯Co 3.176 Å; μ-1,1-OCO- and μ3-OCH3 bridges), J2 = -2.5 cm-1 (Co⋯Co 3.228 Å; μ-1-OCO- and μ3-OCH3 bridges) and J3 = +10.6 cm-1 (Co⋯Co 3.084 Å; two μ3-OCH3 bridges)) have been identified, with the inclusion of the orbital reduction parameter (α = Aκ = 1.38), spin-orbit coupling (λ = -158 cm-1) and axial distortion (energy gap Δ = -975 cm-1 between singlet and doublet levels), rationalized by density functional theory (DFT) calculations.

Manipulating fluorescence by photo-switched spin-state conversions in an iron(ii)-based SCO-MOF.

Manipulating fluorescence by photo-switched spin-state conversions is an attractive prospect for applications in smart magneto-optical materials and devices. The challenge is how to modulate the energy transfer paths of the singlet excited state by light-induced spin-state conversions. In this work, a spin crossover (SCO) FeII-based fluorophore was embedded into a metal-organic framework (MOF) to tune the energy transfer paths. Compound 1 {Fe(TPA-diPy)[Ag(CN)2]2}·2EtOH (1) has an interpenetrated Hofmann-type structure, wherein the FeII ion is coordinated by a bidentate fluorophore ligand (TPA-diPy) and four cyanide nitrogen atoms and acts as the fluorescent-SCO unit. Magnetic susceptibility measurements revealed that 1 underwent an incomplete and gradual spin crossover with T1/2 = 161 K. Photomagnetic studies confirmed photo-induced spin state conversions between the low-spin (LS) and high-spin (HS) states, where the irradiation of 532 and 808 nm laser lights converted the LS and HS states to the HS and LS states, respectively. Variable-temperature fluorescence spectra study revealed an anomalous decrease in emission intensity upon the HS → LS transition, confirming the synergetic coupling between the fluorophore and SCO units. Alternating irradiation of 532 and 808 nm laser lights resulted in reversible fluorescence intensity changes, confirming spin state-controlled fluorescence in the SCO-MOF. Photo-monitored structural analyses and UV-vis spectroscopic studies demonstrated that the photo-induced spin state conversions changed energy transfer paths from the TPA fluorophore to the metal-centered charge transfer bands, ultimately leading to the switching of fluorescence intensities. This work represents a new prototype compound showing bidirectional photo-switched fluorescence by manipulating the spin states of iron(ii).