Molecular Flexibility in Solvated Crystals of the Dimer, Au2(µ-1,2-bis(diphenylphosphino)ethane)2I2, with Three-Coordinate Gold(I).

We report the ability to trap the dimer Au2(µ-dppe)2I2 (dppe is 1,2-bis(diphenylphosphino)ethane) with different separations between the three-coordinate gold ions in crystalline solvates. All of these solvates ((Au2(µ-dppe)2I2·4(CH2Cl2) (1), Au2(µ-dppe)2I2·2(CH2Cl2) (2), the polymorphs α-Au2(µ-dppe)2I2·2(HC(O)NMe2) (3) and ß-Au2(µ-dppe)2I2·2(HC(O)NMe2) (4), and Au2(µ-dppe)2I2·4(CHCl3) (5)) along with polymeric {Au(µ-dppe)I}n·n(CHCl3) (6)) originated from the same reaction, only the solvent system used for crystallization differed. In the different solvates of Au2(µ-dppe)2I2, the Au···Au separation varied from 3.192(1) to 3.7866(3) Å. Computational studies undertaken to understand the flexible nature of these dimers indicated that the structural differences were primarily a result of crystal packing effects with aurophillic interactions having a minimal effect.

Covalently linked thieno[2,3-b]thiophene-fullerene dimers: synthesis and physical characterization.

Thienothiophene (TT) has received great attention in the fields of electronics and optoelectronics. Here we report a synthesis and characterization of fullerene-donor-fullerene triads linked to thieno[2,3-b]thiophene as a donor. The photophysical and electrochemical properties of the new dumbbells were investigated using UV-vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and square wave voltammetry. The results showed that both compounds have higher LUMO energy levels than PC61BM, indicating that they can be used in photovoltaic applications. Furthermore, the powder was structurally and morphologically characterized via X-ray diffraction (XRD) and scanning electron microscopy (SEM). The SEM revealed the morphological characterization of the two derivatives as globular and urchin-like supramolecular assemblies.

Reactions of Thianthrene and 10-Phenylphenothiazine with the Lewis Acids─Titanium Tetrachloride, Titanium Tetrabromide, Tin(IV) Tetrachloride, or Antimony(V) Pentachloride: The Competition between Coordination and Oxidation.

The oxidation of thianthrene and 10-phenylphenothiazine into cation radicals has been examined using redox-active Lewis acids. The reaction of titanium(IV) tetrachloride with thianthrene in toluene produces a solution with an EPR spectrum indicative of oxidation of thianthrene to a cation radical, but the molecular compound (1) (µ-thianthrene)Ti2(µ-Cl2)Cl6 crystallized exclusively. Red crystalline (2) (µ-thianthrene)Ti2(µ-Br2)Br6 formed similarly from titanium(IV) tetrabromide. In contrast, the reaction of antimony(V) pentachloride with thianthrene in toluene yielded crystalline (3) (thianthrene·+)2(Sb2(µ-Cl)2Cl62-)·(SbCl3), while the same reaction in acetonitrile produced crystals of (4) (thianthrene·+)(SbCl6-). The two paramagnetic salts differ in that in (3), the folded (thianthrene·+) cation radicals self-associate, whereas in (4), the (thianthrene·+) cation radicals are isolated from one another and are planar. The reaction of 10-phenylphenothiazine with titanium(IV) tetrachloride in toluene solution resulted in the formation of crystalline paramagnetic (5) (10-phenylphenothiazine·+)(Ti(µ-Cl)3Cl6-) and the reaction of 10-phenylphenothiazine with tin(IV) tetrachloride produced paramagnetic (6) (10-phenylphenothiazine·+)(SnCl5-).

Structure and Luminescence Studies of Salts of the Helical Dication, [Au2(µ-bis(diphenylphosphine)ethane)2]2+ and Comparison with Salts of [Au2(µ-bis(diphenylphosphine)propane)2]2.

Six salts ([Au2(µ-dppe)2](BF4)2·CHCl3, [Au2(µ-dppe)2](BF4)2·1,2-Cl2C2H4, [Au2(µ-dppe)2](PF6)2·CHCl3, [Au2(µ-dppe)2](PF6)2, [Au2(µ-dppe)2](SbF6)2, and [Au2(µ-dppe)2](OTf)2·2CHCl3), (dppe is bis(diphenylphosphine)ethane) containing the dication, [Au2(µ-dppe)2]2+, have been prepared and structurally characterized by single-crystal X-ray crystallography. Unlike the three-coordinate dppe-bridged dimers, Au2X2(µ-dppe)2 (X = Br, I), which show considerable variation in the distance between the gold(I) ions over the range 3.0995(10) to 3.8479(3) Å in various solvates, the structure of the helical dication, [Au2(µ-dppe)2], in the new salts is remarkably consistent with the Au···Au separation falling in the narrow range 2.8787(9) to 2.9593(5) Å. In the solid state, the six crystals display a green luminescence both at room temperature and at 77 K, which has been assigned as phosphorescence. However, solutions of the dication are not luminescent. Salts containing the analogous dication [Au2(µ-dppp)2](PF6)2 (dppp is bis(diphenylphosphine)propane) have been prepared to determine whether the longer bridging ligand might also twist into a helical shape. These salts include [Au2(µ-dppp)2](OTf)2 (OTf is triflate) and three crystalline forms of [Au2(µ-dppp)2](PF6)2: the solvate [Au2(µ-dppp)2](PF6)2·(CHCl3) and two polymorphs of the unsolvated salt. None of these crystals are luminescent, but all contain a similar dication, [Au2(µ-dppp)2]2+, that contains two nearly parallel, linear P-Au-P groups and a long separation between the gold ions that varies from 5.3409(4) to 5.6613(6)Å.

Tb2O@C2(13333)-C74: A Non-Isolated Pentagon Endohedral Fullerene Containing a Nearly Linear Tb-O-Tb Unit.

Terbium has been added to the list of elements that form oxide clusters inside fullerene cages. Tb2O@C2(13333)-C74 has been isolated as a byproduct of the electric arc synthesis of the azafullerene Tb2@C79N. Cocrystallization of Tb2O@C2(13333)-C74 with Ni(OEP) (where OEP is the dianion of octaethylporphyrin) in toluene yielded black needles of Tb2O@C2(13333)-C74·NiII(OEP)·1.5C7H8 that have been examined by single-crystal X-ray diffraction. The resulting structure shows that a nearly linear Tb-O-Tb unit is contained in a C2(13333)-C74, which has two sites where pentagons share an edge to form pentalene units at opposite ends of the fullerene. Unlike the usual situations where metal atoms in fullerenes that do not obey the isolated pentagon rule are situated within the folds of the pentalene units, the Tb atoms in Tb2O@C2(13333)-C74 are positioned to the side of the pentalene units and near-neighboring hexagons. The magnetic properties of Tb2O@C2(13333)-C74 have been examined starting from the experimental geometry, using ab-initio multiconfigurational methods. The computations predict that Tb2O@C2(13333)-C74 will show strong axiality, which would make it a single-molecule magnet with a large magnetic anisotropy barrier.

Self-Assembled Encapsulation of CuX2- (X = Br, Cl) in a Gold Phosphine Box-like Cavity with Metallophilic Au-Cu Interactions.

Synthetic routes to the crystallization of two new box-like complexes, [Au6(Triphos)4(CuBr2)](OTf)5·(CH2Cl2)3·(CH3OH)3·(H2O)4 (1) and [Au6(Triphos)4 (CuCl2)](PF6)5·(CH2Cl2)4 (2) (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine), have been developed. The two centrosymmetric cationic complexes have been structurally characterized through single-crystal X-ray diffraction and shown to contain a CuX2- (X = Br or Cl) unit suspended between two Au(I) centers without the involvement of bridging ligands. These colorless crystals display green luminescence (λem = 527 nm) for (1) and teal luminescence (λem = 464 nm) for (2). Computational results document the metallophilic interactions that are involved in positioning the Cu(I) center between the two Au(I) ions and in the luminescence.

Patient-reported discrimination among limited-resourced cancer survivors: a brief report.

PURPOSE: Healthcare discrimination has been associated with health disparities including lower cancer screenings, higher medical mistrust, and strained patient-provider relationships. Our study sought to understand patient-reported discrimination among cancer survivors with limited resources living in the United States. DESIGN AND METHODS: We used cross-sectional survey data distributed by the Patient Advocate Foundation (PAF) in 12/2020 and 07/2021. Respondents reported source and reason of healthcare discrimination. Age, sex, race and ethnicity, annual household income, Rural-Urban Commuting Area (RUCA), Area Deprivation Index (ADI), employment status, cancer type, and number of comorbidities were independent variables of interest. The association between these variables and patient-reported healthcare discrimination was estimated using risk ratios (RRs) and 95% confidence intervals (CIs) from a multivariable modified Poisson regression model with robust standard errors. FINDINGS: A total of 587 cancer survivors were included in our analysis. Most respondents were female (72%) and aged ≥56 (62%); while 33% were Black, Indigenous, or Person of Color. Overall, 23% reported receipt of discrimination, with the majority reporting doctor, nurse, or healthcare provider as the source (58%). Most common reasons for discrimination included disease status (42%), income/ability to pay (36%), and race and ethnicity (17%). In the adjusted model, retired survivors were 62% less likely to report discrimination compared to those employed (RR 0.38; 95% CI 0.23-0.64). Additionally, survivors with ≥3 comorbidities were 86% more likely to report discrimination compared to those survivors with no non-cancer comorbidities (RR 1.86; 95% CI 1.26-2.72). IMPLICATIONS: Cancer survivors with limited resources reported substantial discrimination most often from a healthcare provider and most commonly for disease status and income. Discrimination should be mitigated to provide equitable and high-quality cancer care.

Direct Crystallization of Diamine Radical Cations: Carbon-Nitrogen Bond Formation from the Reaction of Triphenylamine with TiCl4 , TiBr4 , or SnCl4 versus Carbon-Carbon Bond Formation with SbCl5.

Direct synthesis of diamine radical cations in crystalline form proceeding through oxidation of triphenylamine followed by the formation of a new C-N bond is reported. Although the oxidative coupling of triphenylamine is well studied, diamine products are rarely captured in their radical cation state. The neutral diamine most frequently obtained from this reaction pathway is N,N,N',N'-tetraphenylbenzidine. Herein, the capture of radical cations of diamines in crystalline form in one step starting with neutral triphenylamine was demonstrated, and the formation of two products (the radical cations of N,N,N',N'-tetraphenyl-1,4-benzenediamine or N,N,N',N'-tetraphenylbenzidine) depending on the oxidizing agent used was observed. The radical species are characterized by single-crystal X-Ray diffraction, electron paramagnetic resonance spectroscopy, and optical spectroscopy.

Quantifying treatment preferences and their association with financial toxicity in women with breast cancer.

BACKGROUND: The objective of the current study was to understand treatment preferences and their association with financial toxicity in Patient Advocate Foundation clients with breast cancer. METHODS: This choice-based conjoint analysis used data from a nationwide sample of women with breast cancer who received assistance from the Patient Advocate Foundation. Choice sets created from 13 attributes of 3 levels each elicited patient preferences and trade-offs. Latent class analysis segmented respondents into distinct preference archetypes. The Comprehensive Score for Financial Toxicity (COST) tool captured financial toxicity. Adjusted generalized linear models estimated COST score differences by preference archetype. RESULTS: Of 220 respondents (for a response rate of 10%), the median age was 58 years (interquartile range, 49-66 years); 28% of respondents were Black, indigenous, or people of color; and approximately 60% had household incomes <$40,000. The majority of respondents were diagnosed with early-stage cancer (91%), 38% had recurrent disease, and 61% were receiving treatment. Treatment choice was most affected by preferences related to affordability and impact on activities of daily living. Two distinct treatment preference archetypes emerged. The "cost-prioritizing group" (75% of respondents) was most concerned about affordability, impact on activities of daily living, and burdening care partners. The "functional independence-prioritizing group" (25% of respondents) was most concerned about their ability to work, physical side effects, and interference with life events. COST scores were found to be similar between the archetypes in adjusted models (cost-prioritizing group COST score, 12 [95% confidence interval, 9-14]; and functional independence-prioritizing COST score, 11 [95% confidence interval, 9-13]). CONCLUSIONS: Patients with breast cancer prioritized affordability or maintaining functional independence when making treatment decisions. Because of this variability, preference evaluation during treatment decision making could optimize patients' treatment experiences.

Role of Anions and Mixtures of Anions on the Thermochromism, Vapochromism, and Polymorph Formation of Luminescent Crystals of a Single Cation, [(C6H11NC)2Au].

Noncoordinating anions, which generally play a subordinate role in coordination chemistry, alter the structure, the luminescence, as well as the thermochromic and vapochromic behaviors of salts of the two-coordinate cation, [(C6H11NC)2Au]+. Thus whereas the yellow polymorphs of [(C6H11NC)2Au](PF6) and [(C6H11NC)2Au](AsF6) contain single chains of cations and are vapochromic, yellow [(C6H11NC)2Au](SbF6) does not form the same polymorph and is not vapochromic but contains two distinct chains of cations connected through aurophilic interactions. Mixed crystals such as [(C6H11NC)2Au](PF6)0.50(AsF6)0.50 have been prepared by adding diethyl ether to a dichloromethane solution containing equimolar amounts of [(C6H11NC)2Au](PF6) and [(C6H11NC)2Au](AsF6). The initial (kinetic) product for the three combinations of anions ((PF6)-/(AsF6)-, (PF6)-/(SbF6)-, and (AsF6)-/(SbF6)-) was a precipitate of fine yellow needles with a green emission, which were gradually transformed at rates that depended on the anions present into colorless crystals with a blue emission. Whereas neither polymorph of [(C6H11NC)2Au](PF6) nor [(C6H11NC)2Au](SbF6) is thermochromic, the colorless mixed crystal [(C6H11NC)2Au](PF6)0.50(SbF6)0.50 is thermochromic and converts from blue-emitting to green-emitting at 87-95 °C. The temperature required to transform a crystal of the type [(C6H11NC)2Au](PF6)n(AsF6)1-n from colorless (blue-emitting) to yellow (green-emitting) increases as the fraction of hexafluorophosphate ion in the crystal increases. The yellow crystals of [(C6H11NC)2Au](PF6)0.75(AsF6)0.25, [(C6H11NC)2Au](PF6)0.50(AsF6)0.50, and [(C6H11NC)2Au](PF6)0.25(AsF6)0.75 are vapochromic, whereas the yellow crystals of [(C6H11NC)2Au](PF6)0.50(SbF6)0.50 and [(C6H11NC)2Au](AsF6)0.50(SbF6)0.50 are not.

A Pilot Study of a Comprehensive Financial Navigation Program in Patients With Cancer and Caregivers.

BACKGROUND: Few studies have engaged patients and caregivers in interventions to alleviate financial hardship. We collaborated with Consumer Education and Training Services (CENTS), Patient Advocate Foundation (PAF), and Family Reach (FR) to assess the feasibility of enrolling patient-caregiver dyads in a program that provides financial counseling, insurance navigation, and assistance with medical and cost of living expenses. METHODS: Patients with solid tumors aged ≥18 years and their primary caregiver received a financial education video, monthly contact with a CENTS counselor and PAF case manager for 6 months, and referral to FR for help with unpaid cost of living bills (eg, transportation or housing). Patient financial hardship and caregiver burden were measured using the Comprehensive Score for Financial Toxicity-Patient-Reported Outcomes (COST-PRO) and Caregiver Strain Index (CSI) measures, respectively, at baseline and follow-up. RESULTS: Thirty patients (median age, 59.5 years; 40% commercially insured) and 18 caregivers (67% spouses) consented (78% dyad participation rate). Many participants faced cancer-related financial hardships prior to enrollment, such as work change or loss (45% of patients; 39% of caregivers) and debt (64% of patients); 39% of caregivers reported high levels of financial burden at enrollment. Subjects received $11,000 in assistance (mean, $772 per household); 66% of subjects with income ≤$50,000 received cost-of-living assistance. COST-PRO and CSI scores did not change significantly. CONCLUSIONS: Patient-caregiver dyads were willing to participate in a financial navigation program that addresses various financial issues, particularly cost of living expenses in lower income participants. Future work should address financial concerns at diagnosis and determine whether doing so improves patient and caregiver outcomes.

Quality Measurement in Cancer Care: A Review and Endorsement of High-Impact Measures and Concepts.

Although oncology care has evolved, outcome assessment remains a key challenge. Outcome measurement requires identification and adoption of a succinct list of metrics indicative of high-quality cancer care for use within and across healthcare systems. NCCN established an advisory committee, the NCCN Quality and Outcomes Committee, consisting of provider experts from NCCN Member Institutions and other stakeholders, including payers and patient advocacy, community oncology, and health information technology representatives, to review the existing quality landscape and identify contemporary, relevant cancer quality and outcomes measures by reevaluating validated measures for endorsement and proposing new measure concepts to fill crucial gaps. This manuscript reports on 22 measures and concepts; 15 that align with existing measures and 7 that are new.

Unsymmetrical Coordination of Bipyridine in Three-Coordinate Gold(I) Complexes.

The unsymmetrical coordination of gold(I) by 2,2'-bipyridine (bipy) in some planar, three-coordinate cations has been examined by crystallographic and computational studies. The salts [(Ph3P)Au(bipy)]XF6 (X = P, As, Sb) form an isomorphic series in which the differences in Au-N distances range from 0.241(2) to 0.146(2) Å. A second polymorph of [(Ph3P)Au(bipy)]AsF6 has also been found. Both polymorphs exhibit similar structures. The salts [(Et3P)Au(bipy)]XF6 (X = P, As, Sb) form a second isostructural series. In this series the unsymmetrical coordination of the bipy ligand is maintained, but the gold ions are disordered over two unequally populated positions that produce very similar overall structures for the cations. Although many planar, three-coordinate gold(I) complexes are strongly luminescent, the salts [(R3P)Au(bipy)]XF6 (R = Ph or Et; X = P, As, Sb) are not luminescent as solids or in solution. Computational studies revealed that a fully symmetrical structure for [(Et3P)Au(bipy)]+ is 7 kJ/mol higher in energy than the observed unsymmetrical structure and is best described as a transition state between the two limiting unsymmetrical geometries. The Au-N bonding has been examined by natural resonance theory (NRT) calculations using the "12 electron rule". The dominant Lewis structure is one with five lone pairs on Au and one bond to the P atom, which results in a saturated (12 electron) gold center and thereby inhibits the formation of any classical, 2 e- bonds between the gold and either of the bipy nitrogen atoms. The nitrogen atoms may instead donate a lone pair into an empty Au-P antibonding orbital, resulting in a three-center, four-electron (3c/4e) P-Au-N bond. The binuclear complex, [µ2-bipy(AuPPh3)2](PF6)2, has also been prepared and shown to have an aurophillic interaction between the two gold ions, which are separated by 3.0747(3) Å. Despite the aurophillic interaction, this binuclear complex is not luminescent.

The Preparation of Luminescent, Mechanochromic Molecular Containers from Non-Emissive Components: The Box Cations, [Au6 (Triphos)4 Br]5+ and [Au6 (Triphos)4 Br2 ]4.

Two new molecular boxes, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, and the dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, have been prepared in crystalline form. Although constructed from non-luminescent components, both are strongly luminescent. Like its chloro counterpart, the mono-bromo box [Au6 (Triphos)4 Br](SbF6 )5 ⋅6(CH2 Cl2 ), 4 mB, is mechanochromic. Under grinding, it loses its luminescence. The bromo-bridged helicate, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3µ-H, with a cation that is isomeric with the box [Au6 (Triphos)4 Br]5+ , has also been prepared and crystallographically characterized. Unlike its chloro analogue, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ) is not luminescent. Thus, the cation produced upon grinding may be the cation present in the bromo-bridged helicate, [(µ-Br){Au3 (Triphos)2 }2 ](CF3 SO3 )5 ⋅2(CH2 Cl2 ), 3µ-H. The dibromo box, [Au6 (Triphos)4 Br2 ⋅H2 O](SbF6 )4 ⋅4(CH2 Cl2 ), 5 dB, is not significantly mechanochromic.

Cleavage of Carbon Disulfide by n-Propyldiphenylphosphine and Nickel(II) Bromide.

Carbon disulfide is cleaved by n-propyldiphenylphosphine and nickel(II) bromide in a one-step process, to form two unprecedented complexes: orange, [Ni(S2 C2 (Pn PrPh2 )2 )Br(Pn PrPh2 )]Br⋅CS2 (1) and purple [Ni{η2 -SC(Pn PrPh2 )2 }Br(Pn PrPh2 )]Br⋅0.5CS2 (2). Orange (1) contains a dithiolene-related ligand that results from carbon-carbon bond formation, while purple (2) contains a remarkable ligand in which two n-propyldiphenylphosphine molecules have added to a carbon atom of a CS unit that is coordinated to nickel.

Vapoluminescent Behavior and the Single-Crystal-to-Single-Crystal Transformations of Chloroform Solvates of [Au2 (µ-1,2-bis(diphenylarsino)ethane)2 ](AsF6 )2.

The mono- and di-chloroform solvates of [Au2 (µ-1,2-bis(diphenylarsino)ethane)2 ](AsF6 )2 undergo single-crystal-to-single-crystal transformations that result in gain (over 12 hours) or slow loss (over five years) of only one chloroform molecule. The change in solvation results in changes in the structure and luminescence of the digold cation. The cation consists of a pair of slightly bent As-Au-As units that are connected through the two bridging dpae ligands and by aurophilic interactions with Au⋅⋅⋅Au contacts of 3.05152(15) Šin the disolvate or 2.9570(5) Šin the monosolvate.

Isolation and Crystallographic Characterization of Two, Nonisolated Pentagon Endohedral Fullerenes: Ho3 N@C2 (22010)-C78 and Tb3 N@C2 (22010)-C78.

Purified samples of Ho3 N@C2 (22010)-C78 and Tb3 N@C2 (22010)-C78 have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho2 O3 or Tb4 O7 . Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C2 (22010)-C78 cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C-C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho3 N or Tb3 N unit is planar. Ho3 N@C2 (22010)-C78 and Tb3 N@C2 (22010)-C78 use the same cage previously found for Gd3 N@C2 (22010)-C78 rather than the IPR-obeying cage found in Sc3 N@D3h -C78 .

United States Valuation of EQ-5D-5L Health States Using an International Protocol.

OBJECTIVE: To derive a US-based value set for the EQ-5D-5L questionnaire using an international, standardized protocol developed by the EuroQol Group. METHODS: Respondents from the US adult population were quota-sampled on the basis of age, sex, ethnicity, and race. Trained interviewers guided participants in completing composite time trade-off (cTTO) and discrete choice experiment (DCE) tasks using the EuroQol Valuation Technology software and routine quality control measures. Data were modeled using a Tobit model for cTTO data, a mixed logit model for DCE data, and a hybrid model that combined cTTO and DCE data. Model performance was compared on the basis of logical ordering of coefficients, statistical significance, parsimony, and theoretical considerations. RESULTS: Of 1134 respondents, 1062, 1099, and 1102 respondents provided useable cTTO, DCE, and cTTO or DCE responses, respectively, on the basis of quality control criteria and interviewer judgment. Respondent demographic characteristics and health status were similar to the 2015 US Census. The Tobit model was selected as the preferred model to generate the value set. Values ranged from -0.573 (55 555) to 1 (11 111), with 20% of all predicted health states scores less than 0 (ie, worse than dead). CONCLUSIONS: A societal value set for the EQ-5D-5L was developed that can be used for economic evaluations and decision making in US health systems. The internationally established, standardized protocol used to develop this US-based value set was recommended by the EuroQol Group and can facilitate cross-country comparisons.

Utilization of a Nonemissive Triphosphine Ligand to Construct a Luminescent Gold(I)-Box That Undergoes Mechanochromic Collapse into a Helical Complex.

Luminescent gold(I) complexes ([Au6(Triphos)4Cl](PF6)5·2(CH3C6H5), [Au6(Triphos)4Cl](AsF6)5·8(CH3C6H5), and [Au6(Triphos)4Cl](SbF6)5·7(CH3C6H5) where Triphos = bis(2-diphenylphosphinoethyl)phenylphosphine) with a boxlike architecture have been prepared and crystallographically characterized. A chloride ion resides at the center of the box with two of the six gold(I) ions nearby. Mechanical grinding of blue luminescent crystals containing the cation, [Au6(Triphos)4Cl]5+, results in their conversion into amorphous solids with green emission that contain the bridged helicate cation, [µ-Cl{Au3(Triphos)2}2]5+. A mechanism of the mechanochromic transformation is proposed. The structures of the blue-emitting helicate, [Au3(Triphos)2](CF3SO3)3·4(CH3C6H5)·H2O, and the green-emitting bridged-helicate, [µ-Cl{Au3(Triphos)2}2](PF6)5·3CH3OH have been determined by single crystal X-ray diffraction.

Identifying a Needle in a Haystack: Isolation and Structural Characterization of Er2 C94 as the Carbide Er2 C2 @D3 (85)-C92.

A method has been developed for isolating a pure sample of Er2 C94 from the myriad of fullerenes and endohedral fullerenes that are formed in the electric arc process. Crystallographic analysis of Er2 C94 in a cocrystal formed with Ni(OEP) reveals that the molecule is the carbide Er2 C2 @D3 (85)-C92 . Crystals of Er2 C2 @D3 (85)-C92 ⋅Ni(octaethylporphyrin)⋅2 C7 H8 are isostructural with those of Sm2 @D3 (85)-C92 ⋅Ni(octaethylporphyrin)⋅2 (chlorobenzene). Comparisons are made between the four crystallographically characterized endohedrals (Er2 C2 @D3 (85)-C92 , Gd2 C2 @D3 (85)-C92 , La2 C2 @D3 (85)-C92 , and Sm2 @D3 (85)-C92 ) that utilize the chiral D3 (85)-C92 cage.