Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF 4) 2 •6 H 2 Oi nd ifferent nitriles yields one-dimensional coordination polymers [Fe(ebtz) 2 (RCN) 2 ](BF 4) 2 •nRCN (n = 2f or R = CH 3 (1)a nd n = 0f or R = C 2 H 5 (2)C 3 H 7 (3), C 3 H 5 (4), CH 2 Cl (5)) exhibiting spin crossover (SCO). SCO in 1 and 3-5 is complete and occurs above 160 K. In 2,i ti ss hifted to lower temperatures and is accompanied by wide hysteresis (T 1/2 fl = 78 K, T 1/2 › = 123 K) and proceeds extremelyslowly.Isothermal (80 K) time-resolved single-crystal X-ray diffraction studies revealed ac omplex nature for the HS!LS transition in 2.A n initial, slow stage is associatedw ith shrinkageo fp olymeric chains and with reduction of volume at 77 %(in relation to the differenceb etween cell volumes V HS ÀV LS)w hereas only 16 %o fi ron(II)i ons change spin state. In the second stage, an abruptS CO occurs, associated with breathing of the crystal lattice along the direction of the Fe-nitrile bonds, while the nitriles reorient. HS!LS switchingt riggered by light (808 nm) reveals the couplingo fs pin state and nitrile orientation.T he importance of this coupling was confirmed by studies of [Fe(ebtz) 2 (C 2 H 5 CN/C 3 H 7 CN) 2 ](BF 4) 2 mixed crystals (2a, 2b), showing as hift of T 1/2 to higher values and narrowing of the hysteresis loop concomitantw ith an increase of the fraction of butyronitrile. This increase reduces the capability of nitrile molecules to reorient. Densityf unctional theory(DFT) studies of modelso f1-5 suggest ap articular possibility of 2 to adopt al ow (140-1458)v alue of its Fe-N-C(propionitrile) angle.

Structural phase transition in [Fe(bbtre)₃](ClO₄)₂·2CH₃CN (bbtre = 1,4-di(1-ethyl-1,2,3-triazol-5-yl)butane) plays the role of a switch, allowing spin crossover to be carried out in two ways.

The resistance of Candida albicans and other pathogenic yeasts to azole antifungal drugs has increased rapidly in recent years and is a significant problem in clinical therapy. The current state of pharmacological knowledge precludes the withdrawal of azole drugs, as no other active substances have yet been developed that could effectively replace them. Therefore, one of the anti-yeast strategies may be therapies that can rely on the synergistic action of natural compounds and azoles, limiting the use of azole drugs against candidiasis. Synergy assays performed in vitro were used to assess drug interactions Fractional Inhibitory Concentration Index. The synergistic effect of fluconazole (1) and three synthetic lactones identical to those naturally occurring in celery plants—3-n-butylphthalide (2), 3-n-butylidenephthalide (3), 3-n-butyl-4,5,6,7-tetrahydrophthalide (4)—against Candida albicans ATCC 10231, C. albicans ATCC 2091, and C. guilliermondii KKP 3390 was compared with the performance of the individual compounds separately. MIC90 (the amount of fungistatic substance (in µg/mL) inhibiting yeast growth by 90%) was determined as 5.96–6.25 µg/mL for fluconazole (1) and 92–150 µg/mL for lactones 2–4. With the simultaneous administration of fluconazole (1) and one of the lactones 2–4, it was found that they act synergistically, and to achieve the same effect it is sufficient to use 0.58–6.73 µg/mL fluconazole (1) and 1.26–20.18 µg/mL of lactones 2–4. As fluconazole and phthalide lactones show synergy, 11 new fluconazole analogues with lower toxicity and lower inhibitory activity for CYP2C19, CYP1A2, and CYP2C9, were designed after in silico testing. The lipophilicity was also analyzed. A three-carbon alcohol with two rings was preserved. In all compounds 5–15, the 1,2,4-triazole rings were replaced with 1,2,3-triazole or tetrazole rings. The hydroxyl group was free or esterified with phenylacetic acid or thiophene-2-carboxylic acid chlorides or with adipic acid. In structures 11 and 12 the hydroxyl group was replaced with the fragment -CH2Cl or = CH2. Additionally, the difluorophenyl ring was replaced with unsubstituted phenyl. The structures of the obtained compounds were determined by 1H NMR, and 13C NMR spectroscopy. Molecular masses were established by GC-MS or elemental analysis. The MIC50 and MIC90 of all compounds 1–15 were determined against Candida albicans ATCC 10231, C. albicans ATCC 2091, AM 38/20, C. guilliermondii KKP 3390, and C. zeylanoides KKP 3528. The MIC50 values for the newly prepared compounds ranged from 38.45 to 260.81 µg/mL. The 90% inhibitory dose was at least twice as high. Large differences in the effect of fluconazole analogues 5–15 on individual strains were observed. A synergistic effect on three strains—Candida albicans ATCC 10231, C. albicans ATCC 2091, C. guilliermondii KKP 339—was observed. Fractional inhibitory concentrations FIC50 and FIC90 were tested for the most active lactone, 3-n-butylphthalide, and seven fluconazole analogues. The strongest synergistic effect was observed for the strain C. albicans ATCC 10231, FIC 0.04–0.48. The growth inhibitory amount of azole is from 25 to 55 µg/mL and from 3.13 to 25.3 µg/mL for 3-n-butylphthalide. Based on biological research, the influence of the structure on the fungistatic activity and the synergistic effect were determined.

The reaction between 1,1′-di(tetrazol-1-ylo)methane (1ditz) and iron(II) tetrafluoroborate carried out in the presence of adiponitrile (ADN) afforded the coordination compound [Fe2(μ-1ditz)4(μ-ADN)(ADN)2](BF4)4·2ADN. The 1ditz molecules bridge the Fe(II) ions in two directions, resulting in a polymeric layer, whereas adiponitrile molecules join 1ditz-based units, extending the structure into the three-dimensional network. One of the two axial coordination sites of Fe(II) is occupied by monodentately coordinating adiponitrile. Dinitrile can also act as guest molecules occupying the area between the 1ditz-based layers. Cooling from room temperature triggers the structural phase transitions HS(P1; a, b, c) → HS(P2; 2a, b, c) → LS(P3; a, b, c) (P, phase; HS, high spin; and LS, low spin) associated with the conformational changes of the adiponitrile molecules. In the cooling mode, T 1/2 ↓ = 160 K, while in the heating mode T 1/2 ↑ is equal to 185 K. Depending on the further path of change of the temperature, it is possible (i) to perform the same cooling/heating cycle (T 1/2 ↓ = 160 K; T 1/2 ↑ = 185 K) after the sample is reheated above 240 K or (ii) to execute the cooling with T 1/2 ↓ = 167 K after the heating is stopped at 190 K, where the phase with superlattice (P2) does not appear. Both ways are reversible, and they are managed by conformational changes of the adiponitrile molecules.

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