Validating the Use of Percent Grammatical Utterances for Assessing Mandarin-Speaking Children's Grammatical Skill: Evidence From 3-Year-Olds.

PURPOSE: The study examined the use of percent grammatical utterances (PGUs) for assessing grammatical skills in Mandarin-speaking 3-year-old children. METHOD: Participants were 30 Mandarin-speaking 3-year-olds with typical development. Language samples were collected in two visits for each child using a picture description task. Children were asked to talk about 16 pictures in response to questions and prompts at each visit. Pictures for the language sample collection were identical across the visits. PGUs were computed, and the grammatical errors that children produced in the task were coded and tallied for error types at each visit. Test-retest reliability, split-half reliability, and concurrent criterion validity of PGUs were evaluated. RESULTS: The mean PGU level was approximately 78% at Visit 1 and 81% at Visit 2, both of which were significantly below the mastery level (i.e., 90%). The correlation coefficient for test-retest reliability of PGU was large (r = .70, p < .01); the correlation coefficient for split-half reliability was medium at Visit 1 (r = .47, p < .01) and large (r = .65, p < .01) at Visit 2. In addition, the correlation coefficient for concurrent criterion validity of PGU was medium for both visits (rs ≥ .35, ps ≤ .03). The ranking and proportion of each error type were similar between the visits. CONCLUSION: The initial evidence from psychometric properties suggests that PGU computed from the picture description task is a reliable and valid measure for evaluating grammatical skills in Mandarin-speaking 3-year-old children. SUPPLEMENTAL MATERIAL: https://doi.org/10.23641/asha.25395499.

Downregulation of peripheral luteinizing hormone rescues ovariectomy-associated cognitive deficits in APP/PS1 mice.

Alzheimer's disease (AD) is more prevalent in women than men, supposing due to the decline of estrogens in menopause, accompanied by increased gonadotropins such as luteinizing hormone (LH). We and others found that the transcription factor early growth response-1 (EGR1) regulates cholinergic function including the expression of acetylcholinesterase (AChE) and plays a significant role in cognitive decline of AD. Here we investigated in APP/PS1 mice by ovariectomy (OVX) and estradiol (E2) supplementation or inhibition of LH the effect on hippocampus-related cognition and related molecular changes. We found that OVX-associated cognitive impairment was accompanied by increased dorsal hippocampal EGR1 expression, which was rescued by downregulating peripheral LH rather than by supplementing E2. We also found in postmortem AD brains a higher expression of pituitary LH-mRNA and higher EGR1 expression in the posterior hippocampus. Both, in human and mice, there was a significant positive correlation between respectively posterior/dorsal hippocampal EGR1 and peripheral LH expression. We conclude that peripheral increased LH and increased posterior hippocampal EGR1 plays a significant role in AD pathology.

Noun and Verb Lexicons Differentially Predict Later Grammatical Development in Mandarin-Speaking Children With and Without Late Language Emergence.

PURPOSE: The current investigation evaluated the extent to which early noun, verb, and adjective lexicon sizes predicted later grammatical outcomes in Mandarin-speaking children with and without late language emergence (LLE) using a parent report. METHOD: In Study 1, the parents of 24 Mandarin-speaking children with typical language filled out the toddler version of Mandarin-Chinese Communicative Development Inventory-Taiwan (MCDI-T) when these children were 24 and 36 months old. In Study 2, the parents of 23 children with LLE completed the same form when these children were 24, 36, and 48 months old. Noun, verb, and adjective lexicon sizes and grammatical complexity scores were computed from the MCDI-T form for each child. RESULTS: Study 1 showed that verb lexicon size, but not noun or adjective lexicon size, at 24 months predicted grammatical complexity scores at 36 months for children with typical language. Study 2 revealed that noun lexicon size, but not verb or adjective lexicon size, at 24 months predicted grammatical complexity scores at 36 months for children with LLE. Noun lexicon size at 36 months was also the only significant predictor for grammatical complexity scores at 48 months in children with LLE. CONCLUSIONS: Noun and verb lexicon size differentially predicted later grammatical outcomes in young Mandarin-speaking children with and without LLE. The finding suggested that children with LLE may have approached grammatical learning differently from their typical peers due to the small verb lexicon size in the early phase of language development.

Effect of Predicate Types on the Production of Copula "Is" in 2-Year-Old Children Who Speak General American English.

PURPOSE: Prior work has shown that subject types affected the production of copula BE in young children who spoke General American English (GAE). However, the role of predicate types on the production of copula BE remains unclear. This study examined how predicate types affected the production of copula "is" in young GAE-speaking children. METHOD: Seventeen 2-year-old children with typical language development who spoke GAE were included in this study. Children's production rate of copula "is" in sentences with nominal (e.g., The dog is a king ), permanent-adjectival (e.g., The dog is white ), temporary-adjectival (e.g., The dog is very hot ), or locative (e.g., The dog is outside ) predicates was examined using an elicited repetition task. RESULTS: Two-year-old children who spoke GAE were more likely to repeat copula "is" correctly with nominal, permanent-adjectival, and temporary-adjectival predicates than with locative predicates after sentence length was controlled. There were no other significant differences between predicate types. CONCLUSIONS: Overall, locative predicates are the least facilitative for the production of copula "is" as compared to other predicate types. Predicate types, especially locative predicates, should be considered when the clinician creates sentences to evaluate the production of copula BE and to provide intervention for GAE-speaking children. SUPPLEMENTAL MATERIAL: https://doi.org/10.23641/asha.22630726.

Evaluating Different Scoring Systems for a Picture Description Task Among Preschool Children Who Speak African American English.

PURPOSE: Measures of grammatical accuracy are effective measures of children's language skills. However, many measures, such as percent grammatical utterances, were developed for children who speak General American English (GAE) and, therefore, may not be appropriate for students who speak other dialects. This study examines different scoring systems for a picture description task to explore the impact of different systems for children who speak African American English (AAE). METHOD: Eighteen preschool-age children who speak AAE completed a play-based language sample and a picture description task. The Index of Productive Syntax (IPSyn) was calculated for the play-based language samples and used as the reference measure. The picture description task was scored using four scoring systems: an expansive AAE scoring system, a GAE scoring system, and two strategic scoring systems. Scores were compared for each scoring system, and correlations between IPSyn scores and picture description scores were conducted. RESULTS: Scores on the picture description task were highest in the expansive AAE scoring system, followed by scores in the strategic scoring systems, all of which were higher than scores in the GAE scoring system. There was a significant correlation between IPSyn scores and picture description scores when using the GAE scoring system and the strategic scoring systems, but not when using the expansive AAE scoring system. CONCLUSIONS: Different scoring systems affect AAE-speaking preschoolers' scores on measures of grammatical accuracy, and the use of an expansive AAE scoring system, based on lists of nonmainstream features, may diminish the ability to differentiate between children with different ability levels. Future research is needed to refine scoring systems and to explore the validity of different scoring systems for detecting differences between preschoolers who speak AAE, with and without developmental language disorder. SUPPLEMENTAL MATERIAL: https://doi.org/10.23641/asha.21498618.

Characteristics of Early Expressive Vocabulary in Mandarin-Speaking Children With Cochlear Implants.

PURPOSE: The aim of this study is to evaluate whether Mandarin-speaking children with cochlear implants (CIs) demonstrated early lexical composition similar to their hearing peers who were at the same vocabulary level and the extent to which children with CIs were sensitive to linguistic and conceptual properties when developing early lexicon. METHOD: Participants were 77 Mandarin-speaking children with CIs who received CIs before 30 months of age. Their expressive vocabulary was documented using the Infant Checklist of the Early Vocabulary Inventory for Mandarin Chinese 9 or 12 months after CI activation. Percent social words, common nouns, predicates (verbs, adjectives), and closed-class words in total vocabulary were computed for children at different vocabulary levels. Common nouns and verbs were further coded for their word class (noun, verb), word frequency, word length, and imageability to predict how likely a given noun or verb would be produced by children with CIs. RESULTS: Like children with typical hearing, social words were the most dominant category when vocabulary size in children with CIs was smaller than 20 words; common nouns became the most dominant category when the vocabulary size reached 21 words. The difference in percent common nouns and percent predicates (i.e., noun bias) was similar in children with CIs and their hearing peers. In addition, verbs, common words, monosyllabic words, and more imageable words were more likely to be produced by children with CIs than their counterparts. CONCLUSIONS: Mandarin children with CIs showed language-specific patterns in early lexical composition like their hearing peers. They were able to use multiple linguistic and conceptual cues when approaching early expressive vocabulary despite perceptual and processing constraints. SUPPLEMENTAL MATERIAL: https://doi.org/10.23641/asha.21357723.

Vocabulary Growth in Mandarin-Speaking Children With Bilateral Cochlear Implants, Bimodal Stimulation, or Unilateral Cochlear Implants During the First Year After Activation.

PURPOSE: The purpose of this study was to evaluate vocabulary development in Mandarin-speaking children with bilateral cochlear implants (CIs), bimodal stimulation (CI plus hearing aids [HAs]), or unilateral CIs during the first year after CI activation. METHOD: Participants included 23 children with simultaneous bilateral CIs, 23 children with bimodal stimulation, and 15 children with unilateral CIs. They all received CIs before 30 months of age. Parents were asked to endorse words that their child could understand only or understand and say using the Early Vocabulary Inventory for Mandarin Chinese at the day of CI activation and 1, 3, 6, 9, and 12 months after CI activation. Receptive and expressive vocabulary sizes were computed. RESULTS: Growth curve analysis revealed that children with simultaneous bilateral CIs demonstrated faster growth of receptive vocabulary than those with bimodal stimulation, followed by those with unilateral CIs. Moreover, children with simultaneous bilateral CIs reached the 100-word mark for receptive vocabulary earlier than children with bimodal stimulation, followed by those with unilateral CIs. There were no significant differences among the three groups in expressive vocabulary. CONCLUSIONS: Bilateral CIs have an advantage over bimodal stimulation in early receptive vocabulary development in Mandarin, a tone language. HA usage is still recommended for those who receive one CI.

The Contribution of Socioeconomic Status to Children's Performance on Three Grammatical Measures in the Edmonton Narrative Norms Instrument.

Purpose The purpose of this study was to evaluate the relative contribution of socioeconomic status (SES) on three grammatical measures-finite verb morphology composite (FVMC), percent grammatical utterances (PGU), and clausal density-in children between the ages of 4 and 9 years. Method Data for this study were from the normative sample in the Edmonton Narrative Norms Instrument. For 359 children, hierarchical linear regression was performed to evaluate the amount of variance in FVMC, PGU, and clausal density that was uniquely explained by SES after accounting for child chronological age and language status (typical, impaired). Results After child age and language status were controlled, SES was a significant predictor of PGU and clausal density scores, but not of FVMC scores. SES uniquely accounted for 0.5% of variance in PGU scores and 0.8% of variance in clausal density scores. Conclusions Consistent with maturational accounts of children's development of tense markers, results of this study offer evidence that, among grammatical measures, FVMC is uniquely robust to variation in SES. Although significant, the variance of PGU and clausal density scores uniquely accounted for by SES was close to minimum. Clinicians can therefore include these three grammatical measures for assessing children of different socioeconomic backgrounds. Supplemental Material https://doi.org/10.23641/asha.14810484.

Clausal Density Between Ages 4 and 9 Years for the Edmonton Narrative Norms Instrument: Reference Data and Psychometric Properties.

Purpose This study provided reference data and examined psychometric properties for clausal density (CD; i.e., number of clauses per utterance) in children between ages 4 and 9 years from the database of the Edmonton Narrative Norms Instrument (ENNI). Method Participants in the ENNI database included 300 children with typical language (TL) and 77 children with language impairment (LI) between the ages of 4;0 (years;months) and 9;11. Narrative samples were collected using a story generation task, in which children were asked to tell stories based on six picture sequences. CD was computed from the narrative samples. The split-half reliability, concurrent criterion validity, and diagnostic accuracy were evaluated for CD by age. Results CD scores increased significantly between ages 4 and 9 years in children with TL and those with LI. Children with TL produced higher CD scores than those with LI at each age level. In addition, the correlation coefficients for the split-half reliability and concurrent criterion validity of CD scores were all significant at each age level, with the magnitude ranging from small to large. The diagnostic accuracy of CD scores, as revealed by sensitivity, specificity, and likelihood ratios, was poor. Conclusions The finding on diagnostic accuracy did not support the use of CD for identifying children with LI between ages 4 and 9 years. However, given the attested reliability and validity for CD, reference data of CD from the ENNI database can be used for evaluating children's difficulties with complex syntax and monitoring their change over time. Supplemental Material https://doi.org/10.23641/asha.13172129.

Impact of Cognitive Impairment and Dysarthria on Spoken Language in Multiple Sclerosis.

OBJECTIVE: To investigate the impact of cognitive impairment on spoken language produced by speakers with multiple sclerosis (MS) with and without dysarthria. METHOD: Sixty speakers comprised operationally defined groups. Speakers produced a spontaneous speech sample to obtain speech timing measures of speech rate, articulation rate, and silent pause frequency and duration. Twenty listeners judged the overall perceptual severity of the samples using a visual analog scale that ranged from no impairment to severe impairment (speech severity). A 2 × 2 factorial design examined main and interaction effects of dysarthria and cognitive impairment on speech timing measures and speech severity in individuals with MS. Each speaker group with MS was further compared to a healthy control group. Exploratory regression analyses examined relationships between cognitive and biopsychosocial variables and speech timing measures and perceptual judgments of speech severity, for speakers with MS. RESULTS: Speech timing was significantly slower for speakers with dysarthria compared to speakers with MS without dysarthria. Silent pause durations also significantly differed for speakers with both dysarthria and cognitive impairment compared to MS speakers without either impairment. Significant interactions between dysarthria and cognitive factors revealed comorbid dysarthria and cognitive impairment contributed to slowed speech rates in MS, whereas dysarthria alone impacted perceptual judgments of speech severity. Speech severity was strongly related to pause duration. CONCLUSIONS: The findings suggest the nature in which dysarthria and cognitive symptoms manifest in objective, acoustic measures of speech timing and perceptual judgments of severity is complex.

Finite Verb Morphology Composite Between Age 4 and Age 9 for the Edmonton Narrative Norms Instrument: Reference Data and Psychometric Properties.

Purpose The purpose of this study was to provide reference data and evaluate the psychometric properties for the finite verb morphology composite (FVMC) measure in children between 4 and 9 years of age from the database of the Edmonton Narrative Norms Instrument (ENNI; Schneider, Dubé, & Hayward, 2005). Method Participants included 377 children between age 4 and age 9, including 300 children with typical language and 77 children with language impairment (LI). Narrative samples were collected using a story generation task. FVMC scores were computed from the samples. Split-half reliability, concurrent criterion validity, and diagnostic accuracy for FVMC were further evaluated. Results Children's performance on FVMC increased significantly between age 4 and age 9 in the typical language and LI groups. Moreover, the correlation coefficients for the split-half reliability and concurrent criterion validity of FVMC were medium to large (rs ≥ .429, ps < .001) at each age level. The diagnostic accuracy of FVMC was good or acceptable from age 4 to age 7, but it dropped to a poor level at age 8 and age 9. Conclusion With the empirical evidence, FVMC is appropriate for identifying children with LI between age 4 and age 7. The reference data of FVMC could also be used for monitoring treatment progress. Supplemental Material https://doi.org/10.23641/asha.10073183.

Percent Grammatical Utterances Between 4 and 9 Years of Age for the Edmonton Narrative Norms Instrument: Reference Data and Psychometric Properties.

Purpose The purpose of this article was to provide the reference data and evaluate psychometric properties for the percent grammatical utterances (PGU; Eisenberg & Guo, 2013) in children between 4 and 9 years of age from the database of the Edmonton Narrative Norms Instrument (ENNI; Schneider, Dubé, & Hayward, 2005). Method Participants were 377 children who were between 4 and 9 years of age, including 300 children with typical language (TL) and 77 children with language impairment (LI). Narrative samples were collected using the ENNI protocol (i.e., a story generation task). PGU was computed from the samples. Split-half reliability, concurrent criterion validity, and diagnostic accuracy for PGU were further evaluated. Results PGU increased significantly in children between 4 and 9 years of age in both the TL and LI groups. In addition, the correlation coefficients for the split-half reliability and concurrent criterion validity of PGU were all large (rs ≥ .557, ps < .001). The diagnostic accuracy of PGU was also good or acceptable from ages 4 to 9 years. Conclusions With the attested psychometric properties, PGU computed from the ENNI could be used as an assessment tool for identifying children with LI between 4 and 9 years of age. The reference data of PGU could also be used for monitoring treatment progress. Supplemental Material https://doi.org/10.23641/asha.9630590.

A Single-Step Surface Modification of Electrospun Silica Nanofibers Using a Silica Binding Protein Fused with an RGD Motif for Enhanced PC12 Cell Growth and Differentiation.

In this study, a previously known high-affinity silica binding protein (SB) was genetically engineered to fuse with an integrin-binding peptide (RGD) to create a recombinant protein (SB-RGD). SB-RGD was successfully expressed in Escherichia coli and purified using silica beads through a simple and fast centrifugation method. A further functionality assay showed that SB-RGD bound to the silica surface with an extremely high affinity that required 2 M MgCl2 for elution. Through a single-step incubation, the purified SB-RGD proteins were noncovalently coated onto an electrospun silica nanofiber (SNF) substrate to fabricate the SNF-SB-RGD substrate. SNF-SB-RGD was characterized by a combination of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and immunostaining fluorescence microscopy. As PC12 cells were seeded onto the SNF-SB-RGD surface, significantly higher cell viability and longer neurite extensions were observed when compared to those on the control surfaces. These results indicated that SB-RGD could serve as a noncovalent coating biologic to support and promote neuron growth and differentiation on silica-based substrates for neuronal tissue engineering. It also provides proof of concept for the possibility to genetically engineer protein-based signaling molecules to noncovalently modify silica-based substrates as bioinspired material.

Is Putting SUGAR (Sampling Utterances of Grammatical Analysis Revised) Into Language Sample Analysis a Good Thing? A Response to Pavelko and Owens (2017).

Purpose: In this letter, the authors respond to Pavelko and Owens' (2017) newly advanced set of procedures for language sample analysis: Sampling Utterances and Grammatical Analysis Revised (SUGAR). Method: The authors contrast some of the new guidelines for transcription, morpheme segmentation, and language sample elicitation in SUGAR with traditional conventions for language sample analysis (LSA). They address the potential impact of the new guidelines on some of the target measures in SUGAR-mean length of utterances in morphemes (MLUm), words per sentence (WPS), and clauses per sentence (CPS)-and provide their suggestions. Results: Inclusion of partially intelligible utterances in SUGAR may over- or underestimate children's MLUm and reduce the reliability of computing WPS. Counting derivational morphemes and the component morphemes of catenatives (e.g., gonna) may result in overestimation of children's morphosyntactic skills. Conclusion: Further data are needed to determine whether MLUm including derivational morphemes and the component morphemes of catenatives is a better measure of children's morphosyntactic skills than MLUm excluding those morphemes. Pending such data, the authors recommend maintaining traditional LSA conventions and measures. Furthermore, free, fast automated utilities already exist that reduce barriers for clinicians to conduct informative, in-depth LSA.

The Effect of Laminin Surface Modification of Electrospun Silica Nanofiber Substrate on Neuronal Tissue Engineering.

In this study, we first synthesized a slow-degrading silica nanofiber (SNF2) through an electrospun solution with an optimized tetraethyl orthosilicate (TEOS) to polyvinyl pyrrolidone (PVP) ratio. Then, laminin-modified SNF2, namely SNF2-AP-S-L, was obtained through a series of chemical reactions to attach the extracellular matrix protein, laminin, to its surface. The SNF2-AP-S-L substrate was characterized by a combination of scanning electron microscopy (SEM), Fourier transform-infrared (FTIR) spectroscopy, nitrogen adsorption/desorption isotherms, and contact angle measurements. The results of further functional assays show that this substrate is a biocompatible, bioactive and biodegradable scaffold with good structural integrity that persisted beyond 18 days. Moreover, a synergistic effect of sustained structure support and prolonged biochemical stimulation for cell differentiation on SNF2-AP-S-L was found when neuron-like PC12 cells were seeded onto its surface. Specifically, neurite extensions on the covalently modified SNF2-AP-S-L were significantly longer than those observed on unmodified SNF and SNF subjected to physical adsorption of laminin. Together, these results indicate that the SNF2-AP-S-L substrate prepared in this study is a promising 3D biocompatible substrate capable of sustaining longer neuronal growth for tissue-engineering applications.

Eliciting the Language Sample for Developmental Sentence Scoring: A Comparison of Play With Toys and Elicited Picture Description.

Purpose: This study investigated whether language samples elicited during play and description of pictured events would yield the same results for developmental sentence scoring (DSS). Method: Two language samples were elicited from 58 three-year-olds. One sample was elicited during play with a parent, and the other sample was elicited by an examiner asking children to talk about pictured events in response to elicitation questions. Results: DSS scores were not significantly different between the play and event description samples. However, sentence points were significantly higher for the play sample than for the event description sample. Although there was a correlation between sample types for both DSS and sentence points, the correlation for DSS (r = .52) was below an acceptable level, and the correlation for sentence points (r = .71) was at a minimally acceptable level. Agreement between sample types for pass-fail decisions on the DSS scores using the 10th percentile cutoff recommended by Lee (1974) was only moderate (78%). Conclusion: The current study shows that type of language samples could affect DSS and sentence point scores of 3-year-olds and, hence, the passing and failing decisions for their performance on DSS.

Percent Grammatical Responses as a General Outcome Measure: Initial Validity.

Purpose: This report investigated the validity of using percent grammatical responses (PGR) as a measure for assessing grammaticality. To establish construct validity, we computed the correlation of PGR with another measure of grammar skills and with an unrelated skill area. To establish concurrent validity for PGR, we computed the correlation of PGR with a previously validated measure of grammaticality, percent grammatical utterances (PGU), and examined the extent to which PGR and PGU agreed upon pass/fail decisions for children. Method: Participants included 79 3-year-olds from mostly middle socioeconomic status homes. Language samples were elicited by asking children to describe 15 pictures in response to 4 questions per picture. To calculate PGU, children's responses to all 4 questions were segmented into communication units, and each communication unit was evaluated for grammatical errors. To calculate PGR, the entire response to just the first question was evaluated for grammatical errors. Results: PGR scores significantly correlated with a standardized test of grammar (r = .70), but not with a measure of vocabulary (i.e., type-token ratio; r = .11). In addition, PGR scores were significantly correlated with PGU scores (r = .88). Agreement between PGR and PGU was 92% for pass decisions and 94% for fail decisions. Conclusions: The current study establishes the construct validity of PGR as a measure of grammar and supports the use of PGR as a measure to assess grammaticality.

Core-Shell {Mn7⊂(Mn,Cd)12} Assembled from Core {Mn7} Disc.

Postsynthetic decoration of the Mn7, {MnIII⊂MnII6}, core with CdII in the outer shell to form the next generation Mn13Cd6, {MnIII⊂MnIII3MnII3⊂ MnII6CdII6}, core-shell disc was achieved and confirmed by single-crystal X-ray diffraction. The formation of Mn13Cd6 has only been successful with CdII and if the Cd salt is added within the first half hour window when the inner Mn7 has formed. EDX and ICP-AES gave the accurate content and confirm the average found by X-ray diffraction. HR-ESI-MS was even more precise by revealing three prominent molecular species, Mn13Cd6, Mn14Cd5 and Mn15Cd4, having a distribution of metals. The presence of nonmagnetic metal on the periphery reduces the exchange between these clusters as well as the low magnetic moment decreases the dipolar interaction resulting in a paramagnet compared to the ferrimagnetism found for the parent Mn19, {MnIII⊂MnIII3MnII3⊂MnII12}, disc. This study opens the way for the syntheses of heterometallic core-shell clusters in a controllable fashion.

Intermolecular cascade annulations of N-(arylsulfonyl)acrylamides with dual C(sp3)-H bonds: divergent access to indanes and pyrrolidin-2-ones.

A new divergent intermolecular cascade annulation reaction of N-(arylsulfonyl)acrylamides with dual alkyl C(sp3)-H bonds for producing two types of five-membered rings, indanes and pyrrolidin-2-ones, is described. By using cycloalkanes and common alkanes as a one-carbon unit, an intermolecular [4+1] cascade carboannulation of N-(arylsulfonyl)acrylamides was achieved via a sequence of three C-H bond functionalization/aryl migration/desulfonylation that enables the formation of three C-C bonds and one N-H bond. When the one-carbon unit was changed to cycloalkyl ethers, the alternative intermolecular [4+1] cascade heteroannulation reaction occurred and allowed the construction of two C-C bonds and one C-N bond through dual C-H bond functionalization, aryl migration and desulfonylation cascades.

Multifunctional Triple-Decker Inverse 12-Metallacrown-4 Sandwiching Halides.

A family of six triple-decker complexes, {(MX)2[(pz)4]3} (Hpz = 4-nitropyrazole, MX = NaCl, 1; NaBr, 2; NaI, 3; KCl, 4; KBr, 5, and KI, 6), exhibiting inclusion of halides into inverse 12-metallacrown-4 [inv-(12-MCCu(I),pz-4)] array has been realized. Single-crystal X-ray crystallography of each compound reveals a common structural feature consisting of four CuI ions bonded by four pz to form a square metallomacrocycle comprising four metal centers and eight N atoms, thus giving an inv-[12-MCCu(I),pz-4] motif. Two halides are sandwiched by three inv-[12-MCCu(I),pz-4] to form triple-deckers that are further extended in an offset stacking mode by ligand-unsupported cuprophilicity interactions to form a one-dimensional chain structure. Halides are attached to six CuI centers with weak CuI···halogen interaction, resembling anion templates. High-resolution electrospray ionization mass spectrometry reveals that the predominant fragments corresponding to a half of the triple-decker structures of 1-3 exist in solution. Compounds 4, 5, and 6 showed excellent electrocatalytic activities toward the reduction of nitrite and can also be used as selective "turn-off" sensors for Ag(I) in water. The present results will be helpful for the future design and synthesis of functional inverse metallacrowns and their multiple-decker complexes.